The present invention relates to uracil compounds and use thereof.
An object of the present invention is to provide compounds having excellent herbicidal activity.
Recently, a number of herbicides are commercially available and used. However, since there are many kinds of weeds to be controlled and generation thereof occurs over a long period of time, a herbicide is required having higher herbicidal effect, having wider herbicidal spectrum and causing no problem of phytotoxicity on crops.
U.S. Pat. No. 4,859,229 discloses that certain kinds of phenyluracil compounds have herbicidal activity, however, these phenyluracil compounds do not always have sufficient ability as a herbicide. Also WO 97/01541, and WO 98/41093 disclose that kinds of substituted phenoxyphenyl uracil compounds have herbicidal activity, however, the compounds do not always have sufficient ability as a herbicide.
The present inventors have intensively investigated to find compounds having excellent herbicidal activity, and resultantly, found that uracil compounds of the following formula [I] have excellent herbicidal activity, leading to completion of the present invention. Namely, the present invention provides uracil compounds [I] of the formula [I] (hereinafter, referred to as present compound): 
wherein, W represents oxygen, sulfur, imino or C1 to C3 alkylimino, Y represents oxygen, sulfur, imino or C1 to C3 alkylimino, R1 represents C1 to C3 alkyl or C1 to C3 haloalkyl, R2 represents C1 to C3 alkyl, R4 represents hydrogen or methyl, R5 represents hydrogen, C1 to C6 alkyl, C1 to C6 haloalkyl, C3 to C6 alkenyl, C3 to C6 haloalkenyl, C3 to C6 alkynyl, or C3 to C6 haloalkynyl, X1 represents halogen, cyano, or nitro, X2 represents hydrogen or halogen, and each of X3 and X4 independently represents hydrogen, halogen, C1 to C6 alkyl, C1 to C6 haloalkyl, C3 to C6 alkenyl, C3 to C6 haloalkenyl, C3 to C6 alkynyl, C3 to C6 haloalkynyl, C1 to C6 alkoxy C1 to C6 alkyl, C1 to C6 alkoxy, C1 to C6 haloalkoxy, C1 to C6 alkoxycarbonyl C1 to C6 alkoxy or cyano,
and herbicides comprising each of these compounds as an effective component.
Further, the present invention also provides aniline compounds [XXXII]of the formula [XXXII]: 
wherein, W represents oxygen, sulfur, imino or C1 to C3 alkylimino, R17 represents oxygen or sulfur, R4 represents hydrogen or methyl, R5 represents C1 to C6 alkyl, C1 to C6 haloalkyl, C3 to C6 alkenyl, C3 to C6 haloalkenyl, C3 to C6 alkynyl, C3 to C6 haloalkynyl, X1 represents halogen, cyano, or nitro, X2 represents hydrogen or halogen, and each of X3 and X4 independently represents hydrogen, halogen, C1 to C6 alkyl, C1 to C6 haloalkyl, C3 to C6 alkenyl, C3 to C6 haloalkenyl, C3 to C6 alkynyl, C3 to C6 haloalkynyl, C1 to C6 alkoxy C1 to C6 alkyl, C1 to C6 alkoxy, C1 to C6 haloalkoxy, C1 to C6 alkoxycarbonyl C1 to C6 alkoxy or cyano,
compounds [XXXIV] of the formula [XXXIV]: 
wherein, W represents oxygen, sulfur, imino or C1 to C3 alkylimino, R17 represents oxygen or sulfur, R4 represents hydrogen or methyl, R5 represents C1 to C6 alkyl, C1 to C6 haloalkyl, C3 to C6 alkenyl, C3 to C6 haloalkenyl, C3 to C6 alkynyl, or C3 to C6 haloalkynyl, R18 represents C1 to C6 alkyl or phenyl, X1 represents halogen, cyano, or nitro, X2 represents hydrogen or halogen, and each of X3 and X4 independently represents hydrogen, halogen, C1 to C6 alkyl, C1 to C6 haloalkyl, C3 to C6 alkenyl, C3 to C6 haloalkenyl, C3 to C6 alkynyl, C3 to C6 haloalkinyl, C1 to C6 alkoxy C1 to C6 alkyl, C1 to C6 alkoxy group, C1 to C6 haloalkoxy, C1 to C6 alkoxycarbonyl C1 to C6 alkoxy or cyano group, and
compounds [XXXIII] of the formula [XXXIII]: 
wherein, W represents oxygen, sulfur, imino or C1 to C3 alkylimino, R17 represents oxygen or sulfur, R4 represents hydrogen or methyl, R5 represents C1 to C6 alkyl, C1 to C6 haloalkyl, C3 to C6 alkenyl, C3 to C6 haloalkenyl, C3 to C6 alkynyl, or C3 to C6 haloalkynyl, X1 represents halogen, cyano, nitro, X2 represents hydrogen or halogen, and each of X3 and X4 independently represents hydrogen, halogen, C1to C6alkyl, C1 to C6 haloalkyl, C3 to C6 alkenyl, C3 to C6 haloalkenyl, C3 to C6 alkynyl group, C3 to C6 haloalkynyl group, C1 to C6 alkoxy C1 to C6 alkyl, C1 to C6 alkoxy, C1 to C6 haloalkoxy, C1 to C6 alkoxycarbonyl C1 to C6 alkoxy or cyano,
which are useful as intermediates for producing the present compounds.
In the present invention, the C1 to C3 alkylimino represented by W includes methylimino, ethylimino and the like,
the C1 to C3 alkylimino represented by Y includes methylimino, ethylimino and the like,
the C1 to C3 alkyl represented by R1 means methyl, ethyl, propyl, isopropyl, the C1 to C3 haloalkyl represented by R1 includes bromomethyl, chloromethyl, fluoromethyl, dichloromethyl, trichloromethyl, difluoromethyl, trifluoromethyl, pentafluoroethyl, 1,1-difluoroethyl, 3,3,3-trifluoropropyl and the like,
the C1 to C3 alkyl represented by R2 means methyl, ethyl, propyl, isopropyl,
the C1 to C6 alkyl represented by R5 includes methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl and the like, the C1 to C6 haloalkyl represented by R5 includes bromomethyl, chloromethyl, fluoromethyl, dichloromethyl, trichloromethyl, difluoromethyl, chlorodifluoromethyl, bromodifluoromethyl, trifluoromethyl, pentafluoroethyl, 2-fluoroethyl, 1,1-difluoroethyl, 2,2,2-trichloroethyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl and the like, the C3 to C6 alkenyl represented by R5 includes allyl, 1-methylallyl, 1,1-dimethylallyl, 2-methylallyl, 1-butenyl, 2-butenyl, 3-butenyl and the like, the C3 to C6 haloalkenyl represented by R5 includes 1-chloroallyl, 1-bromoallyl, 2-chloroallyl, 3,3-dichloroallyl and the like, the C3 to C6 alkynyl represented by R5 includes 2-propynyl, 1-methyl-2-propynyl, 1,1-dimethyl-2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2-butynyl and the like, the C3 to C6 haloalkynyl represented by R5 includes 3-chloro-2-propynyl, 3-bromo-2-propynyl, 1-fluoro-2-propynyl, 1-chloro-2-propynyl, 1-bromo-2-propynyl, 1-chloro-2-butynyl and the like,
the C1 to C6 alkyl represented by R18 includes methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl and the like,
the halogen represented by X1 means fluorine, chlorine, bromine, iodine,
the halogen represented by X2 means fluorine, chlorine, bromine, iodine,
the halogen represented by X3 and X4 means fluorine, chlorine, bromine, iodine,
the C1 to C6 alkyl represented by X3 and X4 includes methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl and the like, the C1 to C6 haloalkyl represented by X3 and X4 includes bromomethyl, chloromethyl, fluoromethyl, dichloromethyl, trichloromethyl, difluoromethyl, chlorodifluoromethyl, bromodifluoromethyl, trifluoromethyl, pentafluoroethyl, 2-fluoroethyl, 1,1-difluoroethyl, 2,2,2-trichloroethyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl and the like, the C3 to C6 alkenyl represented by X3 and X4 includes allyl, 1-methylallyl, 1,1-dimethylallyl, 2-methylallyl, 1-butenyl, 2-butenyl, 3-butenyl and the like, the C3 to C6 haloalkenyl represented by X3 and X4 includes 1-chloroallyl, 1-bromoallyl, 2-chloroallyl, 3,3-dichloroallyl and the like, the C3 to C6 alkynyl represented by X3 and X4 includes 2-propynyl, 1-methyl-2-propynyl, 1,1-dimethyl-2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2-butynyl and the like, the C3 to C6 haloalkynyl represented by X3 and X4 includes 3-chloro-2-propynyl, 3-bromo-2-propynyl, 1-fluoro-2-propynyl, 1-chloro-2-propynyl, 1-bromo-2-propynyl, 1-chloro-2-butynyl and the like, the C1 to C6 alkoxy C1 to C6 alkyl represented by X3 and X4 includes methoxymethyl, 2-methoxyethyl, 1-methoxyethyl, 3-methoxypropyl, ethoxymethyl, 2-ethoxyethyl, 3-ethoxypropyl, isopropoxymethyl, 2-isopropoxyethyl and the like, the C1 to C6 alkoxy represented by X3 and X4 includes methoxy, ethoxy, propoxy, isopropoxy, butoxy, s-butoxy, t-butoxy and the like, the C1 to C6 haloalkoxy represented by X3 and X4 includes chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, trifluoromethoxy, 2-fluoroethoxy, 2,2,2-trichloroethoxy and the like, the C1 to C6 alkoxycarbonyl C1 to C6 alkoxy represented by X3 and X4 includes methoxycarbonylmethoxy, ethoxycarbonylmethoxy group, 1-methoxycarbonylethoxy, 1-ethoxycarbonylethoxy, 2-methoxycarbonylethoxy, 2-ethoxycarbonylethoxy and the like.
In the present compounds, those are preferable wherein R1 is methyl substituted with fluorine atom(s) such as trifluoromethyl, difluoromethyl and the like, or ethyl substituted with fluorine atom(s) such as pentafluoroethyl, 1,1-difluoroethyl and the like, more preferably trifluoromethyl, R2 is methyl or ethyl, more preferably methyl, R5 is C1 to C3 alkyl such as methyl, ethyl and propyl, more preferably methyl or ethyl, X1 is halogen, more preferably chlorine, X2 is halogen, more preferably fluorine, X3is hydrogen, X4 is hydrogen, W is oxgen, and/or Y is oxgen, from the standpoint of herbicidal activity. The substitution position of W on the benzen ring is preferably ortho position of Y, at this situation, R4 is preferably hydrogen or methyl, more preferably hydrogen.
As the specially prefered compounds, compound wherein R1 is trifluoromethyl, R2 is methyl, R4 is hydrogen, R5 is methyl, X1 is chlorine, X2 is fluorine, X3 is hydrogen, X4 is hydrogen, W is oxgen, Y is oxgen, and the substitution position of W on the benzen ring is ortho position of Y; and compound wherein R1 is trifluoromethyl, R2 is methyl, R4 is hydrogen, R5 is ethyl, X1 is chlorine, X2 is fluorine, X3 is hydrogen, X4 is hydrogen, W is oxgen, Y is oxgen, and the substitution position of W on the benzen ring is ortho position of Y are listed.
In the present compounds, geometrical isomers derived from a double bond, optical isomers derived from asymmetric carbon, and a diastereomer may sometimes present, and the present compound also includes isomers thereof and mixtures of them.
Then, methods for producing the present compounds will be illustrated.
The present compounds can be produced, for example, by the following production methods ((Production Method 1) to (Production Method 6)).
(Production Method 1)
The present compound can be produced by reacting a compound [III] of the formula [III]
wherein, R1, R2, W, Y, X1, X2, X3 and X4 are the same as defined above,
with a compound [IV] of the formula [IV]
wherein, R4 and R5 are the same as defined above, R6 represents a leaving group such as chlorine, bromine, iodine, methanesulfonyloxy, p-toluenesulfonyloxy and the like, in the presence of a base.
This reaction is conducted usually in a solvent, and the reaction temperature is usually from 0 to 200xc2x0 C., preferably 20 to 100xc2x0 C., and the reaction time is usually from an instant to 72 hours.
Regarding the amounts of reagents to be used in the reaction, it is theoretical that the amount of the compound [IV] is 1 mol and the amount of the base is 1 mol based on 1 mol of the compound [III], and the amounts thereof can be changed optionally depending on the reaction condition.
The base to be used includes organic bases such as pyridine, quinoline, benzyldimethylamine, phenetyldimethylamine, N-methylmorpholine, 1,8-diazabicyclo[5.4.0]undec-7-en, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,4-diazabicyclo[2.2.2]octane, 4-dimethylaminopyridine, N,N-dimethylaniline, N,N-diethylaniline, triethylamine, tri-n-propylamine, trilsopropylamine, tri-n-butylamine, diisopropylethylamine and the like, and inorganic bases such as lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydride, potassium hydride, lithium hydroxide and the like.
Examples of the solvent to be used include aliphatic hydrocarbons such as n-hexane, n-heptane, ligroin, cyclohexane, petroleum ether and the like; aromatic hydrocarbons such as benzene, toluene, xylene and the like; aromatic halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, benzotrifluoride and the like; ethers such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diglyme and the like; ketones such as acetone, 2-butanone, methyl isobutyl ketone and the like; esters such as ethyl formate, ethyl acetate, butyl acetate, diethyl carbonate and the like; nitro compounds such as nitromethane, nitrobenzene and the like; nitriles such as acetonitrile, isobutyronitrile and the like; acid amides such as N,N-dimethylformamide, N,N-dimethylacetamide and the like; sulfur compounds such as dimethyl sulfoxide, sulfolane and the like; or mixtures thereof.
After completion of the reaction, the intended present compound can be obtained, for example, by the following operation 1) or 2).
1) A reaction solution is poured into water, this is extracted with an organic solvent, and the resulted organic layer is dried and concentrated.
2) A reaction solution is concentrated itself, or, filtrated if necessary before the filtrate is concentrated.
Further, the resulted present compound can also be purified by a procedure such as chromatography, re-crystallization and the like.
(Production Method 2)
Of the present compounds, the compound [I] wherein W is oxygen can be produced by reacting a compound [VI of the formula [V]
wherein, R1, R2, Y, X1, X2, X3 and X4 are the same as defined above,
with an alcohol compound [VI] of the formula [VI]
wherein, R4, and R5 are the same as defined above, in the presence of a dehydrating reagent.
This reaction is conducted usually in a solvent, and the reaction temperature is usually from xe2x88x9220 to 150xc2x0 C., preferably from 0 to 100xc2x0 C., and the reaction time is usually from an instant to 48 hours.
As the dehydrating reagent, there are listed combinations of triarylphosphines such as triphenylphosphine and the like or trialkylphosphines such as triethylphosphine and the like, and, di(lower alkyl)azodicarboxylates such as diethylazodicarboxylate, diisopropylazodicarboxylate and the like.
Regarding the amounts of reagents to be used in the reaction, the amount of the alcohol compound [VI] is 1 to 3 mol, preferably 1 to 1.5 mol, the amount of the triarylphosphine or trialkylphosphine is 1 to 3 mol, preferably 1 to 1.5 mol, and the amount of the di(lower alkyl)azodicarboxylate is 1 to 3 mol, preferably 1 to 1.2 mol, based on 1 mol of the compound [V]. The ratio of these reagents can be changed optionally depending on the reaction condition.
The solvent to be used in the reaction includes aliphatic hydrocarbons such as n-hexane, n-heptane, ligroin, cyclohexane, petroleum ether and the like; aromatic hydrocarbons such as benzene, toluene, xylene and the like; aromatic halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, benzotrifluoride and the like; ethers such as diethyl ether, diisopropyl ether, dioxane, THF, ethylene glycol dimethyl ether, diglyme and the like; or mixtures thereof.
After completion of the reaction, the intended present compound can be obtained, for example, by the following operation 1) or 2).
1) A reaction solution is poured into water, this is extracted with an organic solvent, and the resulted organic layer is dried and concentrated, and the residue is subjected to chromatography.
2) A reaction solution is concentrated itself, and the residue is subjected to chromatography.
Further, the resulted present compound can also be purified by a procedure such as re-crystallization and the like.
(Production Method 3)
A compound of the present invention can be produced by using a carboxylic acid compound [VII] of the formula [VII]
wherein, R1, R2, R4, W, Y, X1, X2, X3, and X4 are the same as defined above,
and an alcohol compound [VIII] of the formula [VIII]
HOxe2x80x94R5xe2x80x83xe2x80x83[VIII]
wherein, R5 is the same as defined above.
This reaction is conducted by, for example, reacting the carboxylic acid compound [VII] with a chlorinating agent to give an acid chloride (hereinafter, referred to as  less than Process 3-1 greater than ), then, reacting the acid chloride and the compound [VIII] in the presence of a base (hereinafter, referred to as  less than Process 3-2 greater than ).
 less than Process 3-1 greater than 
This reaction is conducted in the absence of a solvent or in a solvent, and the reaction temperature is usually from 0 to 150xc2x0 C., and the reaction time is usually from an instant to 24 hours.
Regarding the amounts of reagents to be used in the reaction, it is theoretical that the amount of the chlorinating agent is 1 mol based on 1 mol of the carboxylic acid compound [VII], and the amounts thereof can be changed optionally depending on the reaction condition.
Examples of the chlorinating agent to be used include thionyl chloride, sulfuryl chloride, phosgene, oxalyl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride and the like.
Examples of the solvent to be used include aliphatic hydrocarbons such as n-hexane, n-heptane, nonane, decane, ligroin, cyclohexane, petroleum ether and the like; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene and the like; aliphatic halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,2,3-trichloropropane and the like; aromatic halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, benzotrifluoride and the like; ethers such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diglyme and the like; or mixtures thereof.
After completion of the reaction, for example, the reaction solution is concentrated, and the residue is used itself in  less than Process 3-2 greater than .
 less than Process 3-2 greater than 
This reaction is conducted in the absence of a solvent or in a solvent, and the reaction temperature is usually from xe2x88x9220 to 100xc2x0 C., and the reaction time is usually from an instant to 24 hours.
Regarding the amounts of reagents to be used in the reaction, it is theoretical that each amount of the alcohol compound [VIII] and the base is 1 mol based on 1 mol of the carboxylic acid compound [VII] used in  less than Process 3-1 greater than , and the amounts thereof can be changed optionally depending on the reaction condition.
Examples of the base to be used include inorganic bases such as sodium hydrogen carbonate, potassium hydrogen carbonate, lithium carbonate, sodium carbonate, potassium carbonate and the like, nitrogen-containing aromatic compounds such as pyridine, quinoline, 4-dimethylaminopyridine, 2-picoline, 3-picoline, 4-picoline, 2,3-lutidine, 2,4-lutidine, 2,5-lutidine, 2,6-lutidine, 3,4-lutidine, 3,5-lutidine, 3-chloropyridine, 2-ethyl-3-methylpyridine, 5-ethyl-2-methylpyridine and the like, tertiary amines such as triethylamine, diisopropylethylamine, tri-n-propylamine, tri-n-butylamine, benzyldimethylamine, phenetyldimethylamine, N-methylmorpholine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,4-diazabicyclo[2.2.2]octane and the like.
Examples of the solvent to be used include aliphatic hydrocarbons such as n-hexane, n-heptane, nonane, decane, ligroin, cyclohexane, petroleum ether and the like; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene and the like; aliphatic halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,2,3-trichloropropane and the like; aromatic halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, benzotrifluoride and the like; ethers such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diglyme and the like; or mixtures thereof.
After completion of the reaction, the intended present compound can be obtained, for example, by the following operation 1) or 2).
1) A reaction solution is poured into water, this is extracted with an organic solvent, and the resulted organic layer is dried and concentrated.
2) A reaction solution is concentrated itself, or, filtrated if necessary before the filtrate is concentrated.
Further, the resulted present compound can also be purified by a procedure such as chromatography, re-crystallization and the like.
This reaction is not limited to the above-mentioned methods, and can also be conducted by a method in which a reaction is conducted in the presence of a condensing agent such as 1,1xe2x80x2-carbonyldiimidazole, 1,3-dicyclohexylcarbodiimide and the like, a method in which a reaction is conducted in the presence of an acid catalyst, and other known methods.
(Production Method 4)
Of the present compounds, the compound [I] wherein X1 is nitro or cyano can be produced by reacting an uracil compound [IX] of the formula [IX]
wherein, R1, R2 and X2 are the same as defined above, R7 represents fluorine, chlorine, bromine or iodine, and X11 represents nitro or cyano,
with a compound [X] of the formula [X]
wherein, R4, R5, W, Y, X3, and X4 are the same as defined above.] in the presence of a base.
This reaction is conducted usually in the absence of a solvent or in a solvent, and the reaction temperature is from 0 to 200xc2x0 C., and the reaction time is usually from an instant to 24 hours.
Regarding the amounts of reagents to be used in the reaction, it is theoretical that the amount of the compound [X] is 1 mol and the amount of the base is 1 mol based on 1 mol of the uracil compound [IX], and the amounts thereof can be changed optionally depending on the reaction condition.
The base to be used includes organic bases such as pyridine, quinoline, benzyldimethylamine, phenetyldimethylamine, N-methylmorpholine, 1,8-diazabicyclo[5.4.0]undec-7-en, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,4-diazabicyclo[2.2.2]octane, 4-dimethylaminopyridine, N,N-dimethylaniline, N,N-diethylaniline, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, diisopropylethylamine and the like, and inorganic bases such as lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydride, potassium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide and the like.
Examples of the solvent to be used include aliphatic hydrocarbons such as n-hexane, n-heptane, ligroin, cyclohexane, petroleum ether and the like; aromatic hydrocarbons such as benzene, toluene, xylene and the like; aromatic halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, benzotrifluoride and the like; ethers such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diglyme and the like; ketones such as acetone, 2-butanone, methyl isobutyl ketone and the like; esters such as ethyl formate, ethyl acetate, butyl acetate, diethyl carbonate and the like; nitro compounds such as nitromethane, nitrobenzene and the like; nitriles such as acetonitrile, isobutyronitrile and the like; acid amides such as N,N-dimethylformamide, N,N-dimethylacetamide and the like; sulfur compounds such as dimethyl sulfoxide, sulfolane and the like; or mixtures thereof.
This reaction may sometimes be accelerated by using a catalyst. As the catalyst, copper iodide, copper bromide, copper chloride, copper powder and the like are listed, and the amount of the catalyst used in the reaction is from 0.0001 to 0.1 mol based on 1 mol of the uracil compound [IX], and the amounts thereof can be changed optionally depending on the reaction condition.
After completion of the reaction, the intended present compound can be obtained, for example, by the following operation 1) or 2).
1) A reaction solution is poured into water, this is extracted with an organic solvent, and the resulted organic layer is dried and concentrated.
2) A reaction solution is concentrated itself, or, filtrated if necessary before the filtrate is concentrated.
Further, the resulted present compound can also be purified by a procedure such as chromatography, re-crystallization and the like.
(Production Method 5)
Of the present compounds, the compound [I] wherein X1 is fluorine, chlorine, bromine or iodine can be produced by the following scheme. 
Wherein, R1, R2, R4, R5, W, X2, X3, and X4 are the same as defined above, X12 represents fluorine, chlorine, bromine or iodine, and Y1 represents oxygen, sulfur, imino or alkylimino.
 less than Process 5-1 greater than : A process for producing the compound [XII] from the compound [XI].
The compound [XII] can be produced, for example, by reducing the compound [XI] using an iron powder in the presence of an acid in a solvent.
This reaction is conducted usually in the absence of a solvent or in a solvent, and the reaction temperature is usually from 0 to 200xc2x0 C., preferably from room temperature to the reflux temperature. The reaction time is usually from an instant to 24 hours.
Regarding the amounts of reagents to be used in the reaction, the amount of the iron powder is from 3 mol to excess and the amount of the acid is 1 to 10 mol based on 1 mol of the compound [XI], and the amounts thereof can be changed optionally depending on the reaction condition.
As the acid to be used, acetic acid and the like are listed.
As the solvent to be used, there are listed, for example, water, acetic acid, ethyl acetate and the like or mixtures thereof.
After completion of the reaction, an intended material can be obtained by a usual post-treatment operation such as by filtrating, then, pouring a reaction solution into water and the deposited crystals are collected by filtration, or, extracting with an organic solvent, neutralization, concentration and the like.
The intended material can also be purified by a procedure such as chromatography, re-crystallization and the like.
 less than Process 5-2 greater than : A process for producing the compound [XIII] from the compound [XII].
The compound [XIII] can be produced by i) diazotizing the compound [XII] in a solvent, then, ii) subsequently, reacting the diazo compound with potassium iodide, copper [I] bromide, copper [I] chloride or a mixture of hydrofluoric acid with boric acid (hereinafter, referred to as hydroborofluoric acid) depending on the intended compound, in a solvent.
In the diazotization reaction of the first step, the reaction temperature is usually from xe2x88x9220 to 20xc2x0 C., and the reaction time is usually from an instant to 5 hours.
Regarding the amounts of reagents to be used in the reaction, it is theoretical that the amount of the diazotization agent is 1 mol based on 1 mol of the compound [XII], and the amounts thereof can be changed optionally depending on the reaction condition.
As the diazotization agent to be used, nitrites such as sodium nitrite, potassium nitrite, isoamyl nitrite, t-butyl nitrite and the like, are listed.
As the solvent to be used, there are listed, for example, acetonitrile, hydrobromic acid, hydrochloric acid, sulfuric acid, water and the like or mixtures thereof.
The reaction solution after completion of the reaction is used as it is in the following reaction.
In the reaction of the second step, the reaction temperature is from 0 to 80xc2x0 C., and the reaction time is usually from an instant to 24 hours.
Regarding the amounts of reagents to be used in the reaction, each amount of potassium iodide, copper [I] bromide, copper [I] chloride or hydroborofluoric acid is from 1 to 3 mol based on 1 mol of the compound [XII], and the amounts thereof can be changed optionally depending on the reaction condition.
When copper [I] bromide is used, the reaction can also be conducted in the presence of copper [II] bromide, and when copper [I] chloride is used, the reaction can also be conducted in the presence of copper [II] chloride.
As the solvent to be used, there are listed, for example, acetonitrile, diethyl ether, t-butyl methyl ether, hydrobromic acid, hydrochloric acid, sulfuric acid water and the like or mixtures thereof.
After completion of the reaction, an intended present compound can be obtained, for example, by the following operation 1) or 2).
1) A reaction solution is poured into water, this is extracted with an organic solvent, and the resulted organic layer is dried and concentrated.
2) A reaction solution is concentrated itself, or, filtrated if necessary before the filtrate is concentrated.
Further, the resulted present compound can also be purified by a procedure such as chromatography, re-crystallization and the like.
(see, Org. Syn. Coll. Vol. 2, 604 (1943), Vol. 1, 136 (1932))
Further, this reaction is not limited to the above-mentioned methods, and production can also be conducted by reacting the compound [XII] with a diazotizing agent in a solvent in the presence of potassium iodide, copper [I] bromide, copper [I] chloride or hydroborofluoric acid depending on the intended compound (see, Heterocycles., 38, 1581 (1994), and the like).
When copper [I] bromide is used, the reaction can also be conducted in the presence of copper [II] bromide, and when copper [I] chloride is used, the reaction can also be conducted in the presence of copper [II] chloride.
(Production Method 6)
The present compound can be produced by reacting an uracil compound [XXXI] of the formula [XXXI]
wherein, R1, R4, R5, W, Y, X1, X2, X3, and X4 are the same as defined above,
with a compound [XXXX] of the formula [XXXX]
R18xe2x80x94R2xe2x80x83xe2x80x83[XXXX]
wherein, R18 represents a leaving group such as chlorine, bromine, iodine, methanesulfonyloxy, p-toluenesulfonyloxy and the like and R2 is the same as defined above, in the presence of a base.
This reaction is conducted usually in the absence of a solvent or in a solvent, and the reaction temperature is usually from 0 to 200xc2x0 C., preferable 20 to 10xc2x0 C., and the reaction time is usually from an instant to 24 hours.
Regarding the amounts of reagents to be used in the reaction, it is theoretical that the amount of the compound [XXXX] is 1 mol and the amount of the base is 1 mol based on 1 mol of the uracil compound [XXXI], and the amounts thereof can be changed optionally depending on the reaction condition.
The base to be used includes organic bases such as pyridine, quinoline, benzyldimethylamine, phenetyldimethylamine, N-methylmorpholine, 1,8-diazabicyclo[5.4.0]undec-7-en, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,4-diazabicyclo[2.2.2]octane, 4-dimethylaminopyridine, N,N-dimethylaniline, N,N-diethylaniline, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, diisopropylethylamine and the like, metal alkoxides such as sodium methoxide, sodium ethoxide, potassium t-butoxide and the like, and inorganic bases such as lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydride, potassium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide and the like.
Examples of the solvent to be used include aliphatic hydrocarbons such as n-hexane, n-heptane, ligroin, cyclohexane, petroleum ether and the like; aromatic hydrocarbons such as benzene, toluene, xylene and the like; aromatic halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, benzotrifluoride and the like; ethers such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diglyme and the like; ketones such as acetone, 2-butanone, methyl isobutyl ketone and the like; esters such as ethyl formate, ethyl acetate, butyl acetate, diethyl carbonate and the like; nitro compounds such as nitromethane, nitrobenzene and the like; nitriles such as acetonitrile, isobutyronitrile and the like; acid amides such as N,N-dimethylformamide, N,N-dimethylacetamide and the like; sulfur compounds such as dimethyl sulfoxide, sulfolane and the like; alcohols such as methanol, ethanol, ethylene glycol, isopropanol, t-butanol and the like; or mixtures thereof.
After completion of the reaction, an intended present compound can be obtained, for example, by the following operation 1) or 2).
1) A reaction solution is poured into water, this is extracted with an organic solvent, and the resulted organic layer is dried and concentrated.
2) A reaction solution is concentrated itself, or, filtrated if necessary before the filtrate is concentrated.
Further, the resulted present compound can also be purified by a procedure such as chromatography, re-crystallization and the like.
The compound [IV], the alcohol compound [VI], the alcohol compound [VIII] and the compound [X] used in the methods for producing the present compound can be produced by known methods, or, commercially available materials are used.
The carboxylic acid compound [VII] can be produced by acid hydrolysis of the present compound [I].
Some of intermediates used in the method for producing the present compound can be produced, for example, by the following production methods ((Intermediate Production Method 1) to (Intermediate Production Method 16)).
(Intermediate Production Method 1)
Of compound [III], the compound wherein W and Y are oxygen or sulfur (i.e. compound [XIX]) and the compound [XIV] can also be produced by a method described in the following scheme. 
Wherein R1, R2, R7, X2, X3, X4 and X12 are the same as defined above, each of R5 and R7 independently represents oxygen or sulfur, and R16 represents a protective group such as silyl group such as t-butyldimethylsilyl and the like; C1 to C6 alkyl which may be substituted such as t-butyl, methyl and the like; benzyl which may be substituted such as benzyl and the like; methoxymethyl, acetyl, methoxycarbonyl, ethoxycarbonyl and the like.
 less than Process A1-1 greater than : A process for producing the compound [XIV] from the compound [XXXXI]
The compound [XIV] can be produced by reacting the compound [XXXXI] with the compound [XXXXII] in the presence of a base.
This reaction is conducted usually in the absence of a solvent or in a solvent, and the reaction temperature is usually from 0 to 200xc2x0 C., and the reaction time is usually from an instant to 24 hours.
Regarding the amounts of reagents to be used in the reaction, it is theoretical that the amount of the compound [XXXXII] is 1 mol and the amount of the base is 1 mol based on 1 mol of the compound [XXXXI], and the amounts thereof can be changed optionally depending on the reaction condition.
The base to be used includes organic bases such as pyridine, quinoline, benzyldimethylamine, phenetyldimethylamine, N-methylmorpholine, 1,8-diazabicyclo[5.4.0]undec-7-en, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,4-diazabicyclo[2.2.2]octane, 4-dimethylaminopyridine, N,N-dimethylaniline, N,N-diethylaniline, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, diisopropylethylamine and the like, and inorganic bases such as lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydride, potassium hydride, and the like.
Examples of the solvent to be used include aliphatic hydrocarbons such as n-hexane, n-heptane, ligroin, cyclohexane, petroleum ether and the like; aromatic hydrocarbons such as benzene, toluene, xylene and the like; aromatic halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, benzotrifluoride and the like; ethers such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diglyme and the like; ketones such as acetone, 2-butanone, methyl isobutyl ketone and the like; esters such as ethyl formate, ethyl acetate, butyl acetate, diethyl carbonate and the like; nitro compounds such as nitromethane, nitrobenzene and the like; nitriles such as acetonitrile, isobutyronitrile and the like; acid amides such as N,N-dimethylformamide, N,N-dimethylacetamide and the like; sulfur compounds such as dimethyl sulfoxide, sulfolane and the like; or mixtures thereof.
After completion of the reaction, an intended material can be obtained, for example, by the following operation 1), 2) or 3).
1) A reaction solution is poured into water, this is extracted with an organic solvent, and the resulted organic layer is dried and concentrated.
2) The reaction mixture is poured into water and the deposited crystals are collected by filtration.
3) A reaction solution is concentrated itself, or, filtrated if necessary before the filtrate is concentrated.
Further, the intended material can also be purified by a procedure such as chromatography, re-crystallization and the like.
 less than Process A1-2 greater than : A process for producing the compound [XVI] from the compound [XIV].
The compound [XVI] can be produced by reacting the compound [XIV] with the compound [XV] in the presence of a base.
This reaction is conducted usually in the absence of a solvent or in a solvent, and the reaction temperature is usually from xe2x88x9220 to 200xc2x0 C., preferable xe2x88x925 to 80xc2x0 C., and the reaction time is usually from an instant to 24 hours.
Regarding the amounts of reagents to be used in the reaction, it is theoretical that the amount of the compound [XV] is 1 mol and the amount of the base is 1 mol based on 1 mol of the compound [XIV], and the amounts thereof can be changed optionally depending on the reaction condition.
The base to be used includes organic bases such as pyridine, quinoline, benzyldimethylamine, phenetyldimethylamine, N-methylmorpholine, 1,8-diazabicyclo[5.4.0]undec-7-en, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,4-diazabicyclo[2.2.2]octane, 4-dimethylaminopyridine, N,N-dimethylaniline, N,N-diethylaniline, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, diisopropylethylamine and the like, and inorganic bases such as lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydride, potassium hydride, lithium hydroxide, and the like.
Examples of the solvent to be used include aliphatic hydrocarbons such as n-hexane, n-heptane, ligroin, cyclohexane, petroleum ether and the like; aromatic hydrocarbons such as benzene, toluene, xylene and the like; aromatic halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, benzotrifluoride and the like; ethers such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diglyme and the like; ketones such as acetone, 2-butanone, methyl isobutyl ketone and the like; esters such as ethyl formate, ethyl acetate, butyl acetate, diethyl carbonate and the like; nitro compounds such as nitromethane, nitrobenzene and the like; nitriles such as acetonitrile, isobutyronitrile and the like; acid amides such as N,N-dimethylformamide, N,N-dimethylacetamide and the like; sulfur compounds such as dimethyl sulfoxide, sulfolane and the like; or mixtures thereof.
After completion of the reaction, an intended material can be obtained, for example, by the following operation 1) or 2).
1) A reaction solution is poured into water, this is extracted with an organic solvent, and the resulted organic layer is washed with hydrochloric acid, then brine, dried and concentrated.
2) A reaction solution is concentrated itself, or, filtrated if necessary before the filtrate is concentrated.
Further, the intended material can also be purified by a procedure such as chromatography, re-crystallization and the like.
 less than Process A1-3 greater than : A process for producing the compound [XVII] from the compound [XVI].
The compound [XVII] can be produced, for example, by reducing the compound [XVI] using an iron powder in the presence of an acid in a solvent.
The reaction temperature is usually from 0 to 20xc2x0 C., preferably from room temperature to the reflux temperature. The reaction time is usually from an instant to 24 hours.
Regarding the amounts of reagents to be used in the reaction, the amount of the iron powder is from 3 mol to excess and the amount of the acid is 1 to 10 mol based on 1 mol of the compound [XVI], and the amounts thereof can be changed optionally depending on the reaction condition.
As the acid to be used, acetic acid and the like are listed.
As the solvent to be used, there are listed, for example, water, acetic acid, ethyl acetate and the like or mixtures thereof.
After completion of the reaction, and intended material can be obtained by usual post-treatment such as by filtrating, then, pouring a reaction solution into water and collecting the produced crystals by filtration, or, subjecting a reaction solution to extraction with an organic solvent, neutralization, concentration and the like.
The intended material can also be purified by a procedure such as chromatography, re-crystallization and the like.
 less than Process Al-4 greater than : A process for producing the compound [XVIII] from the compound [XVII].
The compound [XVIII] can be produced by i) diazotizing the compound [XVII] in a solvent, then, ii) subsequently, reacting the diazo compound with potassium iodide, copper (I) bromide, copper (I) chloride or hydroborofluoric acid in a solvent.
In the diazotization reaction of the first step, the reaction temperature is usually from xe2x88x9220 to 20xc2x0 C., and the reaction time is usually from an instant to 5 hours.
Regarding the amounts of reagents to be used in the reaction, it is theoretical that the amount of the diazotization agent is 1 mol based on 1 mol of a compound of the general formula [XVII], and the amounts thereof can be changed optionally depending on the reaction condition.
As the diazotization agent to be used, nitrites such as sodium nitrite, potassium nitrite, isoamyl nitrite, t-butyl nitrite and the like, are listed.
As the solvent to be used, there are listed, for example, acetonitrile, hydrobromic acid, hydrochloric acid, sulfuric acid, water and the like or mixtures thereof.
The reaction solution after completion of the reaction is used as it is in the following reaction.
In the reaction of the second step, the reaction temperature is from 0 to 80xc2x0 C., and the reaction time is usually from an instant to 24 hours.
Regarding the amounts of reagents to be used in the reaction, each amount of potassium iodide, copper (I) bromide, copper (I) chloride or hydroborofluoric acid is from 1 to 3 mol based on 1 mol of the compound [XVII], and the amounts thereof can be changed optionally depending on the reaction condition. When copper [I] bromide is used, the reaction can also be conducted in the presence of copper (II) bromide, and when copper (I) chloride is used, the reaction can also be conducted in the presence of copper (II) chloride.
As the solvent to be used, there are listed, for example, acetonitrile, diethyl ether, t-butyl methyl ether, hydrobromic acid, hydrochloric acid, sulfuric acid, water and the like or mixtures thereof.
After completion of the reaction, an intended material can be obtained by a usual post-treatment such as by collecting the produced crystals by filtration (if necessary, by adding water), or, extracting with an organic solvent, concentration and the like.
The intended material can also be purified by a procedure such as chromatography, re-crystallization and the like.
Further, this reaction is not limited to the above-mentioned methods, also be conducted by reacting the compound [XVII] with a diazotizing agent in a solvent (for example, acetonitrile, diethyl ether, t-butyl methyl ether, hydrobromic acid, hydrochloric acid, sulfuric acid, water and the like or mixtures thereof) in the presence of potassium iodide, copper (I) bromide, copper (I) chloride or hydroborofluoric acid.
(see, Heterocycles., 38, 1581 (1994), and the like).
 less than Process A1-5 greater than : A process for producing the compound [XIX] from the compound [XVIII].
The compound [XIX] can be produced by de-protecting the compound [XVIII] using boron tribromide, HBr/acetic acid, conc. hydrochloric acid, conc. sulfuric acid or the like according to a method described in Protective Groups in Organic Synthesis (published by A Wiley-Interscience publication).
Herein, in the case the compound [XVIII] wherein R16 is a benzyl which may be substituted such as benzyl, the compound [XIX] can also be produced by hydrogenation of the compound [XVIII] in the presence of a catalyst.
This reaction is usually conducted in a solvent. The reaction temperature is usually from xe2x88x9220 to 150xc2x0 C., preferably from 0 to 50xc2x0 C. The reaction time is usually from an instant to 48 hours. This reaction can also be conducted under positive pressure, and the reaction is usually conducted under a pressure of 1 to 5 atom.
The amount of the catalyst used in this reaction is from 0.001 to 100% by weight based on the compound [XVIII].
As the catalyst to be used in the reaction, anhydrous palladium/carbon, water-containing palladium/carbon, platinum oxide and the like are listed.
The solvent includes carboxylic acids such as formic acid, acetic acid, propionic acid and the like, esters such as ethyl formate, ethyl acetate, butyl acetate, diethyl carbonate and the like; ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and the like; alcohols such as methanol, ethanol, isopropanol, and the like; water, or mixtures thereof.
After completion of the reaction, an intended material can be obtained by a usual post-treatment operation such as by filtrating a reaction solution before concentrating the solution, or, pouring a reaction solution into water before filtrating the produced crystal, or, pouring a reaction solution into water and subjecting the resulted mixture to extraction with an organic solvent, concentration and the like.
The intended material can also be purified by a procedure such as chromatography, re-crystallization and the like.
(Intermediate Production Method 2)
Of compounds [III], the compound wherein W is NH (i.e. compound [XXIII]) can also be produced by a method described in the following scheme. 
Wherein, R1, R2, R7, Y, X1, X2, X3 and X4 are the same as defined above.
 less than Process A2-1 greater than : A process for producing the compound [XXII] from the compound [XX]
The compound [XXII] can be produced by reacting the compound [XX] with the compound [XXI] in the presence of a base.
This reaction is conducted usually in the absence of a solvent or in a solvent, and the reaction temperature is usually from 0 to 200xc2x0 C., and the reaction time is usually from an instant to 24 hours.
Regarding the amounts of reagents to be used in the reaction, it is theoretical that the amount of the compound [XXI] is 1 mol and the amount of the base is 1 mol based on 1 mol of the compound [XX], and the amounts thereof can be changed optionally depending on the reaction condition.
The base to be used includes organic bases such as pyridine, quinoline, benzyldimethylamine, phenetyldimethylamine, N-methylmorpholine, 1,8-diazabicyclo[5.4.0]undec-7-en, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,4-diazabicyclo[2.2.2]octane, 4-dimethylaminopyridine, N,N-dimethylaniline, N,N-diethylaniline, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, diisopropylethylamine and the like, and inorganic bases such as lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydride, potassium hydride, lithium hydroxide, and the like.
Examples of the solvent to be used include aliphatic hydrocarbons such as n-hexane, n-heptane, ligroin, cyclohexane, petroleum ether and the like; aromatic hydrocarbons such as benzene, toluene, xylene and the like; aromatic halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, benzotrifluoride and the like; ethers such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diglyme and the like; ketones such as acetone, 2-butanone, methyl isobutyl ketone and the like; esters such as ethyl formate, ethyl acetate, butyl acetate, diethyl carbonate and the like; nitro compounds such as nitromethane, nitrobenzene and the like; nitriles such as acetonitrile, isobutyronitrile and the like; acid amides such as N,N-dimethylformamide, N,N-dimethylacetamide and the like; sulfur compounds such as dimethyl sulfoxide, sulfolane and the like; or mixtures thereof.
This reaction may sometimes be accelerated by adding a catalyst.
The amount of the catalyst used in the reaction is preferably from 0.0001 to 0.1 mol based on 1 mol of the compound [XX], and the amounts thereof can be changed optionally depending on the reaction condition.
As the catalyst, copper iodide, copper bromide, copper chloride, copper powder and the like are listed.
After completion of the reaction, an intended material can be obtained, for example, by the following operation 1) or 2).
1) A reaction solution is poured into water, this is extracted with an organic solvent, and the resulted organic layer is dried and concentrated.
2) A reaction solution is concentrated itself, or, filtrated if necessary before the filtrate is concentrated.
Further, the intended material can also be purified by a procedure such as chromatography, re-crystallization and the like.
 less than Process A2-2 greater than : A process for producing the compound [XXIII] from the compound [XXII]
The compound [XXIII] can be produced, for example, by reducing the compound [XXII] using an iron powder in the presence of an acid in a solvent.
The reaction temperature is usually from 0 to 20xc2x0 C., preferably from room temperature to the reflux temperature. The reaction time is usually from an instant to 24 hours.
Regarding the amounts of reagents to be used in the reaction, the amount of the iron powder is from 3 mol to excess and the amount of the acid is 1 to 10 mol based on 1 mol of the compound [XXII], and the amounts thereof can be changed optionally depending on the reaction condition.
As the acid to be used, acetic acid and the like are listed.
As the solvent to be used, there are listed, for example, water, acetic acid, ethyl acetate and the like or mixtures thereof.
After completion of the reaction, an intended material can be obtained by a usual post-treatment such as by filtrating, then, collecting the produced crystals by filtration (if necessary, by adding water), or, extracting with an organic solvent, neutralization, concentration and the like.
The intended material can also be purified by a procedure such as chromatography, re-crystallization and the like.
(Intermediate Production Method 3)
Of compounds [III], the compound wherein W is oxygen (i.e. compound [V]) can be produced by a method described in the following scheme. 
Wherein, R1, R2, Y, X1, X2, X3 and X4 are the same as defined above.
The compound [V] can be produced by i) reacting the compound [XXIII] with diazotizing agent in a solvent, then, ii) subsequently, heating the product in an acidic solvent, or, allowing a copper salt to act on the product in the presence of a copper catalyst.
In the reaction of the first step, the reaction temperature is usually from xe2x88x9220 to 10xc2x0 C., and the reaction time is usually from an instant to 5 hours.
Regarding the amounts of reagents to be used in the reaction, it is theoretical that the amount of the diazotization agent is 1 mol based on 1 mol of the compound [XXIII], and the amounts thereof can be changed optionally depending on the reaction condition.
As the diazotization agent to be used, nitrites such as sodium nitrite, potassium nitrite, isoamyl nitrite, t-butyl nitrite and the like, are listed.
As the solvent to be used, there are listed, for example, acetonitrile, hydrochloric acid, hydrobromic acid, sulfuric acid, water and the like or mixtures thereof.
The reaction solution after completion of the reaction is used as it is in the following reaction.
In the heating reaction in an acidic solvent of the second step, the reaction temperature is from 60xc2x0 C. to reflux temperature, and the reaction time is usually from an instant to 48 hours.
As the acidic solvent there are listed, for example, hydrochloric acid, hydrobromic acid, sulfuric acid solution and the like or mixtures thereof.
After completion of the reaction, an intended material can be obtained by usual post-treatment such as by collecting the produced crystals by filtration (if necessary, by adding water), or, extracting with an organic solvent, concentration and the like.
The intended material can also be purified by a procedure such as chromatography, re-crystallization and the like.
The reaction for allowing a copper salt to act in the presence of a copper catalyst in the second step is conducted in a solvent. The reaction temperature is from 0xc2x0 C. to reflux temperature, and the reaction time is from an instant to 24 hours.
Regarding the amounts of reagents to be used in the reaction, the amount of the copper catalyst is 0.001 to 5 mol and the amount of the copper salt is 1 to 100 mol based on 1 mol of the compound [XXIII], and the amounts thereof can be changed optionally depending on the reaction condition.
As the copper catalyst to be used, copper (I) oxide and the like are listed, and as the copper salt, copper (II) sulfate, copper (II) nitrate and the like are listed.
As the solvent, there are listed, for example, water, hydrochloric acid, sulfuric acid and the like or mixtures thereof.
After completion of the reaction, an intended material can be obtained by a usual post-treatment such as by extracting with an organic solvent, concentration and the like.
The intended material can also be purified by a procedure such as chromatography, re-crystallization and the like.
(Intermediate Production Method 4)
The compound [IX] can be produced by a method described in the following scheme. 
Wherein, R1, R2, R7, X2, and X11 are the same as defined above.
The compound [IX] can be produced by diazotizing the compound [XXIV] in a solvent, then, subsequently reacting the diazo compound with a halogenating agent.
 less than The first step(diazotization reaction) greater than 
reaction temperature: from xe2x88x9220 to 20xc2x0 C.
reaction time: from an instant to 5 hours
the amount of the diazotizing agent: from 1 mol to excess based on 1 mol of compound [XXIV]
diazotizing agent: nitrites such as sodium nitrite, isoamyl nitrite, t-butyl nitrite and the like
Solvent: acetonitrile, hydrochloric acid and the like
 less than The second step greater than 
reaction temperature: from 0 to 80xc2x0 C.
reaction time: from an instant to 24 hours
the amounts of the halogenating reagent: from 1 to 3 mol based on 1 mol of compound [XXIV]
halogenating reagent: potassium iodide, copper [I] bromide, copper [I] chloride or hydroborofluoric acid and the like
Solvent: acetonitrile, hydrochloric acid and the like.
The compound [IX] can also be produced by reacting the compound [XXIV] with a diazotizing agent in a solvent in the presence of a halogenating agent.
reaction temperature: from 0 to 80xc2x0 C.
reaction time: from an instant to 48 hours
the amount of the diazotizing agent: from 1 mol to excess based on 1 mol of compound [XXIV]
diazotizing agent: nitrites such as isoamyl nitrite, t-butyl nitrite and the like
the amounts of the halogenating reagent: from 1 to 3 mol based on 1 mol of compound [XXIV]
halogenating reagent: potassium iodide, copper [I] bromide, copper [I] chloride or hydroborofluoric acid and the like
Solvent: acetonitrile and the like.
When copper [I] bromide is used, the reaction can also be conducted in the presence of copper [II] bromide, and when copper [I] chloride is used, the reaction can also be conducted in the presence of copper [II] chloride.
(Intermediate Production Method 5)
Of compounds [X], the compound wherein W is oxygen or sulfur (i.e. compound [XXVI]) can be produced by a method described in the following scheme. 
Wherein, R4, R5, R6, R15, Y, X3 and X4 are the same as defined above.
The compound [XXVI] can be produced by reacting the compound [XXV] with the compound [IV] in a solvent in the presence of a base.
reaction temperature: from 0 to 200xc2x0 C.
reaction time: from an instant to 72 hours
amount of compound [IV]: 1 to 3 mol based on 1 mol of compound [XXV]
amount of a base: 1 to 3 mol based on 1 mol of compound [XXV]
base: triethylamine, potassium carbonate, sodium hydride and the like
solvent: tetrahydrofuran, acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide, methanol, water and the like; or mixtures thereof.
(Intermediate Production Method 6)
Of compounds [X], the compound wherein Y is oxygen or sulfur (i.e. compound [XXX]) can be produced by a method described in the following scheme. 
Wherein, R4, R5, R6, R16, R17, W, n, X3 and X4 have the same meanings as described above.
 less than Process A6-1 greater than : A process for producing the compound [XXVIII] from the compound [XXVII]
The compound [XXVIII] can be produced by reacting the compound [XXVII] with t-butyldimethylsilyl chloride, isobutene, benzyl chloride, benzyl bromide and the like (see, Protective Groups in Organic Synthesis (A Wiley-Interscience publication)).
 less than Process A6-2 greater than : A process for producing the compound [XXIX] from the compound [XXVIII]
The compound [XXIX] can be produced by reacting the compound [XXVIII] with the compound [IV] in a solvent in the presence of a base.
reaction temperature: from 0 to 200xc2x0 C.
reaction time: from an instant to 72 hours
amount of compound [IV]: 1 to 3 mol based on 1 mol of compound [XXVIII]
amount of a base: 1 to 3 mol based on 1 mol of compound [XXVIII]
base: triethylamine, potassium carbonate, sodium hydride and the like
solvent: tetrahydrofuran, acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide, methanol, water and the like; or mixtures thereof
 less than Process A6-3 greater than : A process for producing the compound [XXX] from the compound [XXIX]
The compound [XXX] can be produced by de-protection of the compound [XXIX] according to a method described in xe2x80x9cYuki Kagaku Jikken no Tebiki (published by Manual of Organic Chemical Experiment)xe2x80x9d, vol. 4, (published by Kagaku Dojin sha), Protective Groups in Organic Synthesis (A Wiley-Interscience publication). Specifically, the compound [XXIX] wherein R18 is silyl such as t-butyldimethylsilyl and the like can be de-protected by reacting trifluoroacetic acid or tetrabutylammonium fluoride and the like in a solvent such as methylene chloride, ethyl acetate, water or the like. The compound [XXIX] wherein R18 is benzyl which may be substituted such as benzyl and the like can be de-protected by reacting with hydrogen in the presence of a catalyst.
reaction temperature: xe2x88x9220 to 150xc2x0 C., preferably from 0 to 50xc2x0 C.
reaction time:from an instant to 48 hours
amount of the catalyst: from 0.001 to 100% by weight based on the compound [XXIX]
catalyst: anhydrous palladium/carbon, water-containing palladium/carbon, platinum oxide and the like
solvent: acetic acid, ethyl acetate, methanol and the like
(Intermediate Production Method 7)
Of compounds [XXXI], the compound wherein Y is oxygen or sulfur can be produced by a method described in the following scheme. 
Wherein, R1, R4, R5, R7, R17, W, X1, X2, X3 and X4 are the same as defined above, R18 represents C1 to C6 alkyl (for example, methyl, ethyl and the like) or phenyl, R19 represents C1 to C6 alkyl (for example, methyl, ethyl and the like).
 less than Process A7-1 greater than : A process for producing the compound [XXXII] from the compound [XXXVI]
The compound [XXXII] can be produced by converting the compound [XXXVI] into the compound [XXXVII], then reacting with the compound [XXXVIII] (see, Bioorganic and Medicinal Chemistry Letters, vol. 5, p. 1035, (1995).
 less than Process A7-2 greater than : A process for producing the compound [XXXIII] from the compound [XXXII]
The compound [XXXIII] can be produced by a method according to a known method described in U.S. Pat. No. 4,859,229 and the like from the compound [XXXII].
Specifically, the compound [XXXIII] can be produced by isocyanating the compound [XXXII] in a solvent or in the absence of a solvent.
Isocyanating agent: phosgene, trichloromethyl chloroformate, oxalyl chloride and the like
Amount of isocyanating agent: from 1 mol to excess based on 1 mol of the compound [XXXII]
Solvent: aromatic hydrocarbons such as benzene, toluene and the like, halogenated aromatic hydrocarbons such as chlorobenzene and the like, esters such as ethyl acetate and the like
Reaction Temperature: from room temperature to reflux temperature
Reaction Time: from an instant to 48 hours
After completion of the reaction, an intended material can be obtained by concentrating a reaction solution itself, and the like. This compound can also be purified by an operation such as re-crystallization and the like.
 less than Process A7-3 greater than : A process for producing the compound [XXXIV] from the compound [XXXII]
The compound [XXXIV] can be produced by a method according to a known method described in U.S. Pat. No. 4,879,229 and the like from the compound [XXXII].
Specifically, the compound [XXXIV] can be produced by reacting the compound [XXXII] with a compound [b-4] of the formula [b-4]
wherein, R18 and X12 are the same as defined above, in the presence of a base.
This reaction is usually conducted in a solvent, and also can be conducted in the absence of a solvent. The reaction temperature is usually from xe2x88x9220 to 200xc2x0 C. The reaction time is usually from an instant to 48 hours.
The amount of the compound [b-4] used in the reaction is from 0.5 mol to excess, preferably from 1.0 to 1.2 mol based on 1 mol of the compound [XXXII].
The amount of the base used in the reaction is from 0.5 mol to excess, preferably from 1.0 to 1.2 mol based on 1 mol of the compound [XXXII].
The base includes inorganic bases such as sodium carbonate, sodium hydroxide and the like, organic bases such as pyridine, 4-dimethylaminopyridine, N,N-dimethylaniline, N,N-diethylaniline, triethylamine, diisopropylethylamine and the like.
The solvent include aliphatic halogenated hydrocarbons such as chloroform and the like, ethers such as tetrahydrofuran, 1,4-dioxane and the like, nitrites such as acetonitrile and the like, esters such as ethyl acetate, water or mixtures thereof, and the like.
After completion of the reaction, an intended material can be obtained by a usual post-treatment operation such as by filtrating the reaction solution before concentrating the solution itself, or, pouring the reaction solution into water and collecting the produced crystals by filtration, or, pouring the reaction solution into water and subjecting the mixture to extraction with an organic solvent, concentration and the like. This compound can also be purified by an operation such as re-crystallization, chromatography and the like.
 less than Process A7-4 greater than : A process for producing the compound [XXXIX] from the compound [XXXIII]
The compound [XXXIX] can be produced by a method according to a known method described in U.S. Pat. No. 4,879,229 and the like from the compound [XXXIII] and the compound [XXXV].
Specifically, the compound [XXXIX] can be produced by reacting the compound [XXXIII] with the compound [XXXV] in a solvent in the presence of a base.
Amount of the compound [XXXV]: 0.5 mol to excess, preferably from 0.8 to 1.2 mol based on 1 mol of the compound [XXXIII]
Base: inorganic bases such as sodium hydride and the like, metal alkoxides such as sodium methoxide, sodium ethoxide and the like
Amount of a base: 0.5 mol to excess, preferably from 0.8 to 1.2 mol based on 1 mol of a compound of the general formula [XXXIII]
Solvent: aromatic hydrocarbons such as benzene, toluene and the like; halogenated aromatic hydrocarbons such as chlorobenzene and the like; amides such as N,N-dimethylformamide and the like; ethers such as tetrahydrofuran and the like; halogenated aliphatic hydrocarbons such as chloroform and the like; sulfur compounds such as dimethyl sulfoxide and the like; and mixtures thereof
Reaction temperature: xe2x88x9240xc2x0 C. to solvent reflux temperature
Reaction time: instant to 72 hours
After completion of the reaction, an intended material can be obtained by a post-treatment operation such as by filtrating a reaction solution before concentrating the solution itself, or, adding an acid to a reaction solution and collecting the produced crystals by filtration, or, adding an acid to a reaction solution, then, subjecting the mixture to extraction with an organic solvent, concentration and the like. As the acid to be added, hydrochloric acid, acetic acid, trifluoroacetic acid, p-toluenesulfonic acid, or aqueous solutions thereof and the like. This compound can also be purified by an operation such as re-crystallization, chromatography and the like.
The resulted compound [XXXIX] can also be reacted with the compound [XXXX] according to a method described in (Production Method 6) without conducting post-treatment such as isolation and the like, to produce the present compound.
 less than Process A7-5 greater than : A process for producing the compound [XXXIX] from the compound [XXXIV]
The compound [XXXIX] can be produced by a method according to a known method described in U.S. Pat. No. 4,879,229 and the like from the compound [XXXIV] and the compound [XXXV].
Specifically, the compound [XXXIX] can be produced by reacting the compound [XXXIV] with the compound [XXXV] in the presence of a base.
This reaction is usually conducted in a solvent, and the reaction temperature is usually from xe2x88x9220 to 200xc2x0 C., preferably from 0 to 130xc2x0 C. The reaction time is usually from an instant to 72 hours.
The amount of the compound [XXXV] used in the reaction is from 0.5 mol to excess, preferably from 0.8 to 1.2 mol based on 1 mol of the compound [XXXIV].
The amount of the base used in the reaction is from 0.5 mol to excess, preferably from 0.8 to 1.2 mol based on the compound [XXXIV].
The base includes organic bases such as 4-dimethylaminopyridine, diisopropylethylamine and the like, inorganic bases such as sodium carbonate, potassium carbonate, sodium hydride, potassium hydride and the like, metal alkoxides such as sodium methoxide, sodium ethoxide, potassium t-butoxide and the like.
The solvent includes ketones such as acetone, methyl isobutyl ketone and the like; aliphatic hydrocarbons such as hexane, heptane, petroleum ether and the like; aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene, mesitylene and the like; ethers such as diethyl ether, diisopropyl ether, 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, methyl-t-butyl ether and the like; acid amides such as N,N-dimethylformamide, N,N-dimethylacetamide and the like; tertiary amines such as pyridine, N,N-dimethylaniline, N,N-diethylaniline, triethylamine, diisopropylethylamine and the like; sulfur compounds such as dimethyl sulfoxide, sulfolane and the like; or mixtures thereof and the like.
After completion of the reaction, an intended material can be obtained by a usual post-treatment operation such as by filtrating the reaction solution before concentrating the solution itself, or, adding an acid to the reaction solution and collecting the produced crystals by filtration, or, adding an acid to the reaction solution, then, subjecting the mixture to extraction with an organic solvent, concentration and the like. As the acid to be added, there are listed hydrochloric acid, acetic acid, trifluoroacetic acid, p-toluenesulfonic acid, or aqueous solutions thereof and the like. This compound can also be purified by an operation such as re-crystallization, chromatography and the like.
The resulted compound [XXXIX] can also be reacted with the compound [XXXX] according to the method described in (Production Method 6) without conducting post-treatment such as isolation and the like, to produce the present compound.
(Intermediate Production Method 8)
Of compounds [III], the compound wherein Y and W are oxygen or sulfur can also be produced by a method described in the following scheme. 
Wherein, R1, R2, R15, R16, R17, X2, X3 and X4 are the same as defined above, R20 represents C1 to C6 alkyl which may be substituted such as methyl, ethyl, trifluoromethyl, trichloromethyl and the like, R26 represents C1 to C6 alkyl which may be substituted such as methyl, ethyl and the like, phenyl which may be substituted such as phenyl and the like, or phenyl C1 to C6 alkyl which may be substituted such as benzyl and the like, and X13 represents nitro, fluorine, chlorine, bromine or iodine.
 less than Process A8-1 greater than : A process for producing the compound [a-2] from the compound [a-1]
The compound [a-2] can be produced, for example, by de-protecting the compound [a-1] according to a method described in xe2x80x9cYuki Kagaku Jikken no Tebiki (published by Manual of Organic Chemical Experiment)xe2x80x9d, vol. 4, (published by Kagaku Dojin sha), Protective Groups in Organic Synthesis (A Wiley-Interscience publication), or according to the following method.
This reaction is conducted usually in the absence of a solvent or in a solvent, and the reaction temperature is usually from 0 to 200xc2x0 C., and the reaction time is usually from an instant to 24 hours. Regarding the amounts of reagents to be used in the reaction, it is theoretical that the amount of the reagent is 1 mol based on 1 mol of the compound [a-1], and the amounts thereof can be changed optionally depending on the reaction condition. As the reagent used, boron trifluoride diethyl etherate, boron trifluoride methanol complex, triethyloxoniumtetrafluoro borate and the like are listed. As the solvent used, there are listed aliphatic hydrocarbons such as hexane, heptane, octane, ligroin and the like; aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene, mesitylene and the like; aliphatic halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,2,3-trichloropropane and the like, aromatic halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, benzotrifluoride and the like; ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, methyl-t-butyl ether and the like; alcohols such as methanol, ethanol and the like, or mixtures thereof and the like.
After completion of the reaction, an intended material can be obtained by a post-treatment operation such as by pouring the reaction solution into water, collecting the deposited crystals by filtration and drying them, or, extracting with an organic solvent and drying and concentrating the organic layer, or, concentrating the reaction solution itself, and the like. This compound can also be purified by an operation such as re-crystallization, chromatography and the like.
 less than Process A8-2 greater than : A process for producing the compound [a-3] from the compound [a-2]
The compound [a-3] can be produced by reacting the compound [a-2] with a compound [b-1] of the formula [b-1]
wherein, R26 and X12 are the same as defined above,
in the presence of a base.
This reaction is usually conducted in a solvent, and also can be conducted in the absence of a solvent. The reaction temperature is usually from xe2x88x9220 to 200xc2x0 C. The reaction time is usually from an instant to 48 hours.
The amount of the compound [b-1] used in the reaction is from 0.5 mol to excess, preferably from 1.0 to 1.2 mol based on 1 mol of the compound [a-2].
The amount of the base used in the reaction is from 0.5 mol to excess, preferably from 1.0 to 1.2 mol based on 1 mol of the compound [a-2].
The base includes inorganic bases such as sodium carbonate, sodium hydroxide and the like, organic bases such as pyridine, 4-dimethylaminopyridine, N,N-dimethylaniline, N,N-diethylaniline, triethylamine, diisopropylethylamine and the like.
The solvent include aliphatic halogenated hydrocarbons such as chloroform and the like, ethers such as tetrahydrofuran, 1,4-dioxane and the like, nitrites such as acetonitrile and the like, esters such as ethyl acetate, water or mixtures thereof, and the like.
After completion of the reaction, an intended material can be obtained by a usual post-treatment operation such as by filtrating the reaction solution before concentrating the solution itself, or, pouring the reaction solution into water and collecting the produced crystals by filtration, or, pouring the reaction solution into water and subjecting the mixture to extraction with an organic solvent, concentration and the like. This compound can also be purified by an operation such as re-crystallization, chromatography and the like.
 less than Process A8-3 greater than : A process for producing the compound [a-5] from the compound [a-3]
The compound [a-5] can be produced by reacting the compound [a-3] with the compound [XXXV] in the presence of a base.
This reaction is usually conducted in a solvent, and the reaction temperature is usually from xe2x88x9220 to 200xc2x0 C., preferably from 0 to 130xc2x0 C. The reaction time is usually from an instant to 72 hours.
The amount of the compound [XXXV] used in the reaction is from 0.5 mol to excess, preferably from 0.8 to 1.2 mol based on 1 mol of the compound [a-3].
The amount of the base used in the reaction is from 0.5 mol to excess, preferably from 0.8 to 1.2 mol based on the compound [a-3].
The base includes organic bases such as 4-dimethylaminopyridine, diisopropylethylamine and the like, inorganic bases such as sodium carbonate, potassium carbonate, sodium hydride, potassium hydride and the like, metal alkoxides such as sodium methoxide, sodium ethoxide, potassium t-butoxide and the like.
The solvent includes ketones such as acetone, methyl isobutyl ketone and the like; aliphatic hydrocarbons such as hexane, heptane, petroleum ether and the like; aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene, mesitylene and the like; ethers such as diethyl ether, diisopropyl ether, 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, methyl-t-butyl ether and the like; nitro compounds such as nitromethane, nitrobenzene and the like; acid amides such as N,N-dimethylformamide, N,N-dimethylacetamide and the like; tertiary amines such as pyridine, N,N-dimethylaniline, N,N-diethylaniline, triethylamine, diisopropylethylamine and the like; sulfur compounds such as dimethyl sulfoxide, sulfolane and the like; or mixtures thereof and the like.
After completion of the reaction, an intended material can be obtained by a post-treatment operation such as by filtrating the reaction solution before concentrating the solution itself, or, adding an acid to the reaction solution and collecting the produced crystals by filtration, or, adding an acid to the reaction solution, then, subjecting the mixture to extraction with an organic solvent, concentration and the like. As the acid to be added, there are listed hydrochloric acid, acetic acid, trifluoroacetic acid, p-toluenesulfonic acid, or aqueous solutions thereof and the like. This compound can also be purified by an operation such as chromatography, re-crystallization and the like. Further, the compound [a-5] can also be used in a reaction of the following process without isolation.
 less than Process A8-4 greater than : A process for producing the compound [a-4] from the compound [a-2]
The compound [a-4] can be produced by isocyanating the compound [a-2] by reaction with an isocyanating agent in a solvent or in the absence of a solvent.
Isocyanating agent: phosgene, trichloromethyl chloroformate, oxalyl chloride and the like
Amount of isocyanating agent: from 1 mol to excess based on 1 mol of the compound [a-2]
Solvent: aromatic hydrocarbons such as benzene, toluene and the like, halogenated aromatic hydrocarbons such as chlorobenzene and the like, esters such as ethyl acetate and the like
Reaction Temperature: from room temperature to reflux temperature
Reaction Time: from an instant to 48 hours
After completion of the reaction, an intended material can be obtained by concentrating the reaction solution itself, and the like. This compound can also be purified by an operation such as re-crystallization and the like.
 less than Process A8-5 greater than : A process for producing the compound [a-5] from the compound [a-4]
The compound [a-5] can be produced by reacting the compound [a-4] with the compound [XXXV] in a solvent in the presence of a base.
Amount of the compound [XXXV]: 0.9 to 10 mol based on 1 mol of the compound [a-4]
Base: inorganic bases such as sodium hydride, potassium hydroxide, sodium hydroxide and the like, metal alkoxides such as sodium methoxides, sodium ethoxides and the like
Amount of a base: 0.1 to 10 mol based on 1 mol of the compound [a-4]
Solvent: aromatic hydrocarbons such as benzene, toluene and the like; halogenated aromatic hydrocarbons such as chlorobenzene and the like; amides such as N,N-dimethylformamide and the like; ethers such as tetrahydrofuran and the like; halogenated aliphatic hydrocarbons such as chloroform and the like; sulfur compounds such as dimethyl sulfoxide and the like; and mixtures thereof
Reaction temperature: xe2x88x9240xc2x0 C. to solvent reflux temperature
Reaction time: instant to 72 hours
After completion of the reaction, an intended material can be obtained by a post-treatment operation such as by neutralizing, then, pouring a reaction solution into water, and collecting the deposited crystals and drying them, or, extracting with an organic solvent and drying and concentrating the organic layer, or, concentrating a reaction solution itself, and the like. This compound can also be purified by an operation such as re-crystallization, chromatography and the like.
The resulted compound [a-5] can also be used in a reaction of the following process without isolation.
 less than Process A8-6 greater than : A process for producing the compound [a-6] from the compound [a-5]
The compound [a-6] can be produced by reacting the compound [a-5] with the compound [XXXX] in the presence of a base.
This reaction is usually conducted in a solvent, and the reaction temperature is usually from xe2x88x9220 to 200xc2x0 C., preferably from 0 to 100xc2x0 C. The reaction time is usually from an instant to 48 hours.
The amount of the compound [XXXX] used in the reaction is from 0.5 mol to excess, preferably from 0.8 to 1.2 mol based on 1 mol of the compound [a-5].
The amount of the base used in the reaction is from 0.5 mol to excess, preferably from 0.8 to 1.2 mol based on 1 mol of the compound [a-5].
The base includes organic bases such as pyridine, 4-dimethylaminopyridine, N,N-dimethylaniline, N,N-diethylaniline, triethylamine, diisopropylethylamine and the like, sodium carbonate, potassium carbonate, sodium hydride, potassium hydride and the like.
The solvent include aliphatic hydrocarbons such as hexane, heptane, octane, ligroin, cyclohexane and the like; aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene, mesitylene and the like; ethers such as diethyl ether, diisopropyl ether, 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, methyl-t-butyl ether and the like; nitro compounds such as nitromethane, nitrobenzene and the like; acid amides such as N,N-dimethylformamide, N,N-dimethylacetamide and the like; tertiary amines such as pyridine, N,N-dimethylaniline, N,N-diethylaniline, triethylamine, diisopropylethylamine and the like; sulfur compounds such as dimethyl sulfoxide, sulfolane and the like; alcohols such as methanol, ethanol, ethylene glycol, isopropanol, t-butnol and the like; or mixtures thereof and the like.
After completion of the reaction, an intended material can be obtained by a usual post-treatment operation such as by filtrating a reaction solution before concentrating the solution itself, or, pouring a reaction solution into water and collecting the produced crystals, or, pouring a reaction solution into water, then, subjecting the mixture to extraction with an organic solvent, concentration and the like.
This compound can also be purified by an operation such as chromatography, re-crystallization and the like.
 less than Process A8-7 greater than : A process for producing the compound [a-7] from the compound [a-6].
The compound [a-7] can be produced according to the Process A1-5 of the Intermediate Production Method 1 from the compound [a-6]
(Intermediate Production Method 9)
The compound [a-1] can be produced by a method described in the following scheme. (In the scheme, the compound [a-1] is represented as compound [a-9] or compound [a-11].) 
Wherein R7, R15, R16, R17, R20, X2, X3, X4 and X12 are the same Ad as defined above.
 less than Process A9-1 greater than : A process for producing the compound [a-9] from the compound [a-8]
The compound [a-9] can be produced by reacting the compound [a-8] with the compound [XV] in the presence of a base.
This reaction is conducted usually in the absence of a solvent or in a solvent, and the reaction temperature is usually from 0 to 200xc2x0 C., and the reaction time is usually from an instant to 24 hours.
Regarding the amounts of reagents to be used in the reaction, it is theoretical that the amount of the compound [XV] is 1 mol and the amount of the base is 1 mol based on 1 mol of the compound [a-8], and the amounts thereof can be changed optionally depending on the reaction condition.
The base to be used includes organic bases such as pyridine, quinoline, benzyldimethylamine, phenetyldimethylamine, N-methylmorpholine, 1,8-diazabicyclo[5.4.0]undec-7-en, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,4-diazabicyclo[2.2.2]octane, 4-dimethylaminopyridine, N,N-dimethylaniline, N,N-diethylaniline, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, diisopropylethylamine and the like, metal alkoxides such as sodium methoxide, sodium ethoxide, potassium t-butoxide and the like, and inorganic bases such as lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydride, potassium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide and the like.
Examples of the solvent to be used include aliphatic hydrocarbons such as n-hexane, n-heptane, ligroin, cyclohexane, petroleum ether and the like; aromatic hydrocarbons such as benzene, toluene, xylene and the like; aromatic halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, benzotrifluoride and the like; ethers such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diglyme and the like; ketones such as acetone, 2-butanone, methyl isobutyl ketone and the like; esters such as ethyl formate, ethyl acetate, butyl acetate, diethyl carbonate and the like; nitro compounds such as nitromethane, nitrobenzene and the like; nitriles such as acetonitrile, isobutyronitrile and the like; acid amides such as N,N-dimethylformamide, N,N-dimethylacetamide and the like; sulfur compounds such as dimethyl sulfoxide, sulfolane and the like; alcohols such as methanol, ethanol, ethylene glycol, isopropanol, t-butanol and the like; or mixtures thereof.
After completion of the reaction, an intended material can be obtained, for example, by the following operation 1) or 2).
1) A reaction solution is poured into water, this is extracted with an organic solvent, and the resulted organic layer is dried and concentrated.
2) A reaction solution is concentrated itself, or, filtrated if necessary before the filtrate is concentrated.
Further, the intended material can also be purified by a procedure such as chromatography, re-crystallization and the like.
 less than Process A9-2 greater than : A process for producing the compound [a-10] from the compound [a-9]
The compound [a-10] can be produced, for example, by reducing the compound [a-9] using an iron powder in the presence of an acid in a solvent.
The reaction temperature of this reaction is usually from 0 to 200xc2x0 C., preferably from room temperature to the reflux temperature. The reaction time is usually from an instant to 24 hours.
Regarding the amounts of reagents to be used in the reaction, the amount of the iron powder is from 3 mol to excess and the amount of the acid is 1 to 10 mol based on 1 mol of the compound [a-9], and the amounts thereof can be changed optionally depending on the reaction condition.
As the acid to be used, acetic acid and the like are listed.
As the solvent to be used, there are listed, for example, water, acetic acid, ethyl acetate and the like or mixtures thereof.
After completion of the reaction, an intended material can be obtained by a usual post-treatment such as by pouring a reaction solution into water directly or after filtration and collecting the produced crystals, or, extracting with an organic solvent, neutralization, concentration and the like.
The intended material can also be purified by a procedure such as chromatography, re-crystallization and the like.
 less than Process A9-3 greater than : A process for producing the compound [a-11] from the compound [a-10].
The compound [a-11] can be produced by i) diazotizing the compound [a-10] in a solvent, then, ii) subsequently, reacting the diazo compound with potassium iodide, copper (I) bromide, copper (I) chloride or hydroborofluoric acid in a solvent.
In the diazotization reaction of the first step, the reaction temperature is from xe2x88x9220 to 20xc2x0 C., and the reaction time is usually from an instant to 5 hours.
Regarding the amounts of reagents to be used in the reaction, it is theoretical that the amount of the diazotization agent is 1 mol based on 1 mol of the compound [a-10], and the amounts thereof can be changed optionally depending on the reaction condition.
As the diazotization agent to be used, nitrites such as sodium nitrite, potassium nitrite, isoamyl nitrite, t-butyl nitrite and the like, are listed.
As the solvent, there are listed, for example, acetonitrile, hydrobromic acid, hydrochloric acid, sulfuric acid, water and the like or mixtures thereof.
The reaction solution after completion of the reaction is used as it is in the following reaction.
In the reaction of the second step, the reaction temperature is from 0 to 80xc2x0 C., and the reaction time is usually from an instant to 24 hours.
Regarding the amounts of reagents to be used in the reaction, each amount of potassium iodide, copper (I) bromide, copper (I) chloride or hydroborofluoric acid is from 1 to 3 mol based on 1 mol of the compound [a-10], and the amounts thereof can be changed optionally depending on the reaction condition. When copper [I] bromide is used, the reaction can also be conducted in the presence of copper (II) bromide, and when copper (I) chloride is used, the reaction can also be conducted in the presence of copper (II) chloride.
As the solvent to be used, there are listed, for example, acetonitrile, diethyl ether, t-butyl methyl ether, hydrobromic acid, hydrochloric acid, sulfuric acid, water and the like or mixtures thereof.
After completion of the reaction, an intended material can be obtained by collecting the produced crystals by filtration (if necessary, by adding water), or, extracting with an organic solvent, concentration and the like.
The intended material can also be purified by a procedure such as chromatography, re-crystallization and the like.
Further, this reaction is not limited to the above-mentioned methods, and production can also be conducted by reacting the compound [a-10] with the diazotizing agent in a solvent (for example, acetonitrile, diethyl ether, t-butyl methyl ether, hydrobromic acid, hydrochloric acid, sulfuric acid, water or mixtures thereof) in the presence of potassium iodide, copper (I) bromide, copper (I) chloride or hydroborofluoric acid.
(Intermediate Production Method 10)
The compound [III] wherein X1 is nitro, fluorine, chlorine, bromine or iodine, and Y and W are oxygen or sulfur can also be produced by a method described in the following scheme. 
Wherein, R1, R2, R7, R17, X2, X3, X4 and X12 are the same as defined above.
 less than Process A10-1 greater than : A process for producing the compound [a-12] from the compound [XIV]
The compound [a-12] can be produced by reacting the compound [XIV] with the compound [b-2] of the formula [b-2]
wherein, R17, X3 and X4 are the same as defined above, in the presence of a base.
This reaction is conducted usually in the absence of a solvent or in a solvent, and the reaction temperature is usually from 0 to 200xc2x0 C., and the reaction time is usually from an instant to 24 hours.
Regarding the amounts of reagents to be used in the reaction, it is theoretical that the amount of the compound [b-2] is 1 mol and the amount of the base is 1 mol based on 1 mol of the compound [XIV], and the amounts thereof can be changed optionally depending on the reaction condition.
The base to be used includes organic bases such as pyridine, quinoline, benzyldimethylamine, phenetyldimethylamine, N-methylmorpholine, 1,8-diazabicyclo[5.4.0]undec-7-en, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,4-diazabicyclo[2.2.2]octane, 4-dimethylaminopyridine, N,N-dimethylaniline, N,N-diethylaniline, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, diisopropylethylamine and the like, and inorganic bases such as lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate and the like.
Examples of the solvent to be used include aliphatic hydrocarbons such as n-hexane, n-heptane, ligroin, cyclohexane, petroleum ether and the like; aromatic hydrocarbons such as benzene, toluene, xylene and the like; aromatic halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, benzotrifluoride and the like; ethers such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diglyme and the like; ketones such as acetone, 2-butanone, methyl isobutyl ketone and the like; esters such as ethyl formate, ethyl acetate, butyl acetate, diethyl carbonate and the like; nitro compounds such as nitromethane, nitrobenzene and the like; nitriles such as acetonitrile, isobutyronitrile and the like; acid amides such as N,N-dimethylformamide, N,N-dimethylacetamide and the like; sulfur compounds such as sulfolane and the like; or mixtures thereof.
After completion of the reaction, an intended material can be obtained, for example, by the following operation 1) or 2).
1) A reaction solution is poured into water, this is extracted with an organic solvent, and the resulted organic layer is dried and concentrated.
2) A reaction solution is concentrated itself, or, filtrated if necessary before the filtrate is concentrated.
Further, the intended material can also be purified by a procedure such as chromatography, re-crystallization and the like.
 less than Process A10-2 greater than : A process for producing the compound [a-13] from the compound [a-12]
The compound [a-13] can be produced, for example, by reducing the compound [a-12] using an iron powder in the presence of an acid in a solvent.
The reaction temperature of this reaction is usually from 0 to 200xc2x0 C., preferably from room temperature to the reflux temperature. The reaction time is usually from an instant to 24 hours.
Regarding the amounts of reagents to be used in the reaction, the amount of the iron powder is from 3 mol to excess and the amount of the acid is 1 to 10 mol based on 1 mol of the compound [a-12], and the amounts thereof can be changed optionally depending on the reaction condition.
As the acid to be used, acetic acid and the like are listed.
As the solvent to be used, there are listed, for example, water, acetic acid, ethyl acetate and the like or mixtures thereof.
After completion of the reaction, an intended material can be obtained by pouring a reaction solution into water directly or after filtration and collecting the produced crystals by filtration, or, extracting with an organic solvent, neutralization, concentration and the like.
The intended material can also be purified by a procedure such as chromatography, re-crystallization and the like.
 less than Process A10-3 greater than : A process for producing the compound [a-14] from the compound [a-13].
The compound [a-14] can be produced by i) diazotizing the compound [a-13] in a solvent, then, ii) subsequently, reacting the diazo compound with potassium iodide, copper (I) bromide, copper (I) chloride or hydroborofluoric acid in a solvent.
In the diazotization reaction of the first step, the reaction temperature is from xe2x88x9220 to 20xc2x0 C., and the reaction time is usually from an instant to 5 hours.
Regarding the amounts of reagents to be used in the reaction, it is theoretical that the amount of the diazotization agent is 1 mol based on 1 mol of the compound [a-13], and the amounts thereof can be changed optionally depending on the reaction condition.
As the diazotization agent to be used, nitrites such as sodium nitrite, potassium nitrite and the like, organic nitrous acid compounds such as isoamyl nitrite, t-butyl nitrite and the like, are listed.
As the solvent, there are listed, for example, acetonitrile, hydrobromic acid, hydrochloric acid, sulfuric acid, water and the like or mixtures thereof.
The reaction solution after completion of the reaction is used as it is in the following reaction.
In the reaction of the second step, the reaction temperature is from 0 to 80xc2x0 C., and the reaction time is usually from an instant to 24 hours.
Regarding the amounts of reagents to be used in the reaction, each amount of potassium iodide, copper (I) bromide, copper (I) chloride or hydroborofluoric acid is from 1 to 3 mol based on 1 mol of the compound [a-13], and the amounts thereof can be changed optionally depending on the reaction condition. When copper (I) bromide is used, the reaction can also be conducted in the presence of copper (II) bromide, and when copper (I) chloride is used, the reaction can also be conducted in the presence of copper (II) chloride.
As the solvent to be used, there are listed, for example, acetonitrile, diethyl ether, t-butyl methyl ether, hydrobromic acid, hydrochloric acid, sulfuric acid, water and the like or mixtures thereof.
After completion of the reaction, an intended material can be obtained by collecting the produced crystals (if necessary, by adding water), or, extracting with an organic solvent, concentration and the like.
The intended material can also be purified by a procedure such as chromatography, re-crystallization and the like.
Further, this reaction is not limited to the above-mentioned methods, and production can also be conducted by reacting the compound [a-13] with the diazotizing agent in a solvent (for example, acetonitrile, diethyl ether, t-butyl methyl ether, hydrobromic acid, hydrochloric acid, sulfuric acid, water or mixtures thereof) in the presence of potassium iodide, copper (I) bromide, copper (I) chloride or hydroborofluoric acid.
(Intermediate Production Method 11)
Of the compounds [III], the compound wherein Y and W are oxygen can also be produced by a method described in the following scheme. 
Wherein, R1, R2, R20, X1, X2, X3and X4 are the same as defined above.
 less than Process A11-1 greater than : A process for producing the compound [a-16] from the compound [a-15]
The compound [a-16] can be produced, for example, by de-protecting the compound [a-15] according to a method described in xe2x80x9cYuki Kagaku Jikken no Tebiki (published by Manual of Organic Chemical Experiment)xe2x80x9d, vol. 4, (published by Kagaku Dojin sha), Protective Groups in Organic Synthesis (published by A Wiley-Interscience publication), or according to the following method.
This reaction is conducted usually in the absence of a solvent or in a solvent, and the reaction temperature is usually from 0 to 200xc2x0 C., and the reaction time is usually from an instant to 24 hours. Regarding the amounts of reagents to be used in the reaction, it is theoretical that the amount of the reagent is 1 mol based on 1 mol of the compound [a-15], and the amounts thereof can be changed optionally depending on the reaction condition. As the reagent used, boron trifluoride methanol complex, triethyloxoniumtetrafluoro borate and the like are listed. As the solvent used, there are listed aliphatic hydrocarbons such as hexane, heptane, octane, ligroin and the like; aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene, mesitylene and the like; aliphatic halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, 1,2-a dichloroethane, 1,2,3-trichloropropane and the like, aromatic halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, benzotrifluoride and the like; ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, methyl-t-butyl ether and the like; alcohols such as methanol, ethanol and the like, or mixtures thereof and the like.
After completion of the reaction, an intended material can be obtained by a post-treatment operation such as by pouring a reaction solution into water and collecting the deposited crystals and drying them, or, extracting with an organic solvent and drying and concentrating the organic layer, or, concentrating a reaction solution itself, and the like. This compound can also be purified by an operation such as re-crystallization, chromatography and the like.
 less than Process A11-2 greater than : A process for producing the compound [a-17] from the compound [a-16]
The compound [a-17] can be produced by isocyanating the compound [a-16] by reaction with an isocyanating agent in a solvent or in the absence of a solvent.
Isocyanating agent: phosgene, trichloromethyl chloroformate, oxalyl chloride and the like
Amount of isocyanating agent: from 1 mol to excess based on 1 mol of the compound [a-16]
Solvent: aromatic hydrocarbons such as benzene, toluene and the like, halogenated aromatic hydrocarbons such as chlorobenzene and the like, esters such as ethyl acetate and the like
Reaction Temperature: from room temperature to reflux temperature
Reaction Time: from an instant to 48 hours
After completion of the reaction, an intended material can be obtained by concentrating a reaction solution itself, and the like. This compound can also be purified by an operation such as re-crystallization and the like.
 less than Process A11-3 greater than : A process for producing the compound [a-18] from the compound [a-17]
The compound [a-18] can be produced by reacting the compound [a-17] with the compound [XXXV] in a solvent in the presence of a base.
Amount of the compound [XXXV]: 0.9 to 10 mol based on 1 mol of the compound [a-17]
Base: inorganic bases such as sodium hydride, potassium hydride, sodium hydroxide and the like, metal alkoxides such as sodium methoxide, sodium ethoxide and the in like
Amount of a base: 0.1 to 10 mol based on 1 mol of the compound [a-17]
Solvent: aromatic hydrocarbons such as benzene, toluene and the like; halogenated aromatic hydrocarbons such as chlorobenzene and the like; amides such as N,N-dimethylformamide and the like; ethers such as tetrahydrofuran and the like; halogenated aliphatic hydrocarbons such as chloroform and the like; and mixtures thereof
Reaction temperature: xe2x88x9240xc2x0 C. to solvent reflux temperature
Reaction time: instant to 72 hours
After completion of the reaction, an intended material can be obtained by a post-treatment operation such as by neutralizing, then, pouring a reaction solution into water, and collecting the deposited crystals by filtration, or, extracting with an organic solvent and drying and concentrating the organic layer, or, concentrating a reaction solution itself, and the like. This compound can also be purified by an operation such as re-crystallization, chromatography and the like.
The compound [a-18] can also be used in the reaction of the following process without isolation.
 less than Process A11-4 greater than : A process for producing the compound [a-29] from the compound [a-18]
The compound [a-29] can be produced by reacting the compound [a-18] with the compound [XXXX] in the presence of a base.
This reaction is usually conducted in a solvent, and the reaction temperature is usually from xe2x88x9220 to 200xc2x0 C., preferably from 0 to 100xc2x0 C. The reaction time is usually from an instant to 48 hours.
The amount of the compound [XXXX] used in the reaction is from 0.5 mol to excess, preferably from 0.8 to 1.2 mol based on 1 mol of the compound [a-18].
The amount of the base used in the reaction is from 0.5 mol to excess, preferably from 0.8 to 1.2 mol based on 1 mol of the compound [a-18].
The base includes organic bases such as pyridine, 4-dimethylaminopyridine, N,N-dimethylaniline, N,N-diethylaniline, triethylamine, diisopropylethylamine and the like, sodium carbonate, potassium carbonate, sodium hydride, potassium hydride and the like.
The solvent include aliphatic hydrocarbons such as hexane, heptane, octane, ligroin, cyclohexane, petroleum ether and the like; aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene, mesitylene and the like; ethers such as diethyl ether, diisopropyl ether, 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, methyl-t-butyl ether and the like; nitro compounds such as nitromethane, nitrobenzene and the like; acid amides such as N,N-dimethylformamide, N,N-dimethylacetamide and the like; tertiary amines such as pyridine, N,N-dimethylaniline, -N,N-diethylaniline, triethylamine, diisopropylethylamine and the like; sulfur compounds such as dimethyl sulfoxide, sulfolane and the like; or mixtures thereof and the like.
After completion of the reaction, an intended material can be obtained by a usual post-treatment operation such as by filtrating a reaction solution before concentrating the solution itself, or, pouring a reaction solution into water and collecting the produced crystals, or, pouring a reaction solution into water, then, subjecting the mixture to extraction with an organic solvent, concentration and the like. This compound can also be purified by an operation such as chromatography, re-crystallization and the like.
(Intermediate Production Method 12)
The compound [XXXII] wherein X1 is nitro, fluorine, chlorine, bromine or iodine can also be produced by a method described in the following scheme. 
Wherein, R4, R5, R7, R17, R20, W, X2, X3, X4, X12 and X13 are the same as defined above.
 less than Process A12-1 greater than : A process for producing the compound [a-20] from the compound [a-19]
The compound [a-20] can be produced by reacting the compound [a-19] with a compound [b-3] of the formula [b-3]
wherein, R4, R5, R17, W, Y, X3, and X4 are the same as defined above,
in the presence of a base.
This reaction is conducted usually in the absence of a solvent or in a solvent, and the reaction temperature is usually from 0 to 200xc2x0 C., and the reaction time is usually from an instant to 24 hours.
Regarding the amounts of reagents to be used in the reaction, it is theoretical that the amount of the compound [b-3] is 1 mol and the amount of the base is 1 mol based on 1 mol of the compound [a-19], and the amounts thereof can be changed optionally depending on the reaction condition.
The base to be used includes organic bases such as pyridine, quinoline, benzyldimethylamine, phenetyldimethylamine, N-methylmorpholine, 1,8-diazabicyclo[5.4.0]undec-7-en, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,4-diazabicyclo[2.2.2]octane, 4-dimethylaminopyridine, N,N-dimethylaniline, N,N-diethylaniline, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, diisopropylethylamine and the like, and inorganic bases such as lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydride, potassium hydride and the like.
Examples of the solvent to be used include aliphatic hydrocarbons such as n-hexane, n-heptane, ligroin, cyclohexane, petroleum ether and the like; aromatic hydrocarbons such as benzene, toluene, xylene and the like; aromatic halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, benzotrifluoride and the like; ethers such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diglyme and the like; ketones such as acetone, 2-butanone, methyl isobutyl ketone and the like; esters such as ethyl formate, ethyl acetate, butyl acetate, diethyl carbonate and the like; nitro compounds such as nitromethane, nitrobenzene and the like; nitriles such as acetonitrile, isobutyronitrile and the like; acid amides such as N,N-dimethylformamide, N,N-dimethylacetamide and the like; sulfur compounds such as dimethyl sulfoxide, sulfolane and the like; or mixtures thereof.
After completion of the reaction, an intended material can be obtained, for example, by the following operation 1) or 2).
1) A reaction solution is poured into water, this is extracted with an organic solvent, and the resulted organic layer is dried and concentrated.
2) A reaction solution is concentrated itself, or, filtrated if necessary before the filtrate is concentrated.
Further, the intended material can also be purified by a procedure such as chromatography, re-crystallization and the like.
 less than Process A12-2 greater than : A process for producing the compound [a-21] from the compound [a-20]
The compound [a-21] can be produced, for example, by reducing the compound [a-20] using an iron powder in the presence of an acid in a solvent.
The reaction temperature of this reaction is usually from 0 to 200xc2x0 C., preferably from room temperature to the reflux temperature. The reaction time is usually from an instant to 24 hours.
Regarding the amounts of reagents to be used in the reaction, the amount of the iron powder is from 3 mol to excess and the amount of the acid is 1 to 10 mol based on 1 mol of the compound [a-20], and the amounts thereof can be changed optionally depending on the reaction condition.
As the acid to be used, acetic acid and the like are listed.
As the solvent to be used, there are listed, for example, water, acetic acid, ethyl acetate and the like or mixtures thereof.
After completion of the reaction, an intended material can be obtained by usual post-treatment such as by pouring a reaction solution into water directly or after filtration and collecting the produced crystals by filtration, or, extracting with an organic solvent, neutralization, concentration and the like.
The intended material can also be purified by a procedure such as chromatography, re-crystallization and the like.
 less than Process A12-3 greater than : A process for producing the compound [a-22] from the compound [a-21].
The compound [a-22] can be produced by i) diazotizing the compound [a-21] in a solvent, then, ii) subsequently, reacting the diazo compound with potassium iodide, copper (I) bromide, copper (I) chloride or hydroborofluoric acid in a solvent.
In the diazotization reaction of the first step, the reaction temperature is from xe2x88x9220 to 20xc2x0 C., and the reaction time is usually from an instant to 5 hours.
Regarding the amounts of reagents to be used in the reaction, it is theoretical that the amount of the diazotization agent is 1 mol based on 1 mol of the compound [a-21], and the amounts thereof can be changed optionally depending on the reaction condition.
As the diazotization agent to be used, nitrites such as sodium nitrite, potassium nitrite, isoamyl nitrite, t-butyl nitrite and the like, are listed.
As the solvent, there are listed, for example, acetonitrile, hydrobromic acid, hydrochloric acid, sulfuric acid, water and the like or mixtures thereof.
The reaction solution after completion of the reaction is used as it is in the following reaction.
In the reaction of the second step, the reaction temperature is from 0 to 80xc2x0 C., and the reaction time is usually from an instant to 24 hours.
Regarding the amounts of reagents to be used in the reaction, each amount of potassium iodide, copper (I) bromide, copper (I) chloride or hydroborofluoric acid is from 1 to 3 mol based on 1 mol of the compound [a-21], and the amounts thereof can be changed optionally depending on the reaction condition When copper (I) bromide is used, the reaction can also be conducted in the presence of copper (II) bromide, and when copper (I) chloride is used, the reaction can also be conducted in the presence of copper (II) chloride.
As the solvent to be used, there are listed, for example, acetonitrile, diethyl ether, t-butyl methyl ether, hydrobromic acid, hydrochloric acid, sulfuric acid, water and the like or mixtures thereof.
After completion of the reaction, an intended material can be obtained by usual post-treatment such as collecting the produced crystals (if necessary, by adding water), or, extracting with an organic solvent, concentration and the like.
The intended material can also be purified by a procedure such as chromatography, re-crystallization and the like.
Further, this reaction is not limited to the above-mentioned methods, and production can also be conducted by reacting the compound [a-21] with the diazotizing agent in a solvent (for example, acetonitrile, diethyl ether, t-butyl methyl ether, hydrobromic acid, hydrochloric acid, sulfuric acid, water or mixtures thereof) in the presence of potassium iodide, copper (I) bromide, copper (I) chloride or hydroborofluoric acid.
When copper (I) bromide is used, the reaction can also be conducted in the presence of copper (II) bromide, and when copper (I) chloride is used, the reaction can also be conducted in the presence of copper (II) chloride.
 less than Process A12-4 greater than : A process for producing the compound [a-23] from the compound [a-22]
The compound [a-23] can be produced, for example, by de-protecting the compound [a-22] according to a method described in xe2x80x9cYuki Kagaku Jikken no Tebiki (published by Manual of Organic Chemical Experiment)xe2x80x9d, vol. 4, (published by Kagaku Dojin sha), Protective Groups in Organic Synthesis (published by A Wiley-Interscience publication), or according to the following method.
This reaction is conducted usually in the absence of a solvent or in a solvent, and the reaction temperature is usually from 0 to 200xc2x0 C., and the reaction time is usually from an instant to 24 hours. Regarding the amounts of reagents to be used in the reaction, it is theoretical that the amount of the reagent is 1 mol based on 1 mol of the compound [a-22], and the amounts thereof can be changed optionally depending on the reaction condition. As the reagent used, boron trifluoride methanol complex, triethyloxoniumtetrafluoro borate and the like are listed. As the solvent used, there are listed aliphatic hydrocarbons such as hexane, heptane, octane, ligroin and the like; aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene, mesitylene and the like; aliphatic halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,2,3-trichloropropane and the like, aromatic halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, benzotrifluoride and the like; ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, methyl-t-butyl ether and the like; alcohols such as methanol, ethanol and the like, or mixtures thereof and the like.
After completion of the reaction, an intended material can be obtained by a post-treatment operation such as by pouring a reaction solution into water and collecting the deposited crystals by filtration and drying them, or, extracting with an organic solvent and drying and concentrating the organic layer, or, concentrating a reaction solution itself, and the like. This compound can also be purified by an operation such as re-crystallization, chromatography and the like.
 less than Process A12-5 greater than : A process for producing the compound [a-23] from the compound [a-20]
The compound [a-23] wherein X13 is nitro can be produced according to the method described in  less than Process A12-4 greater than from the compound [a-20].
(Intermediate Production Method 13)
The compound [XXXIV] and the compound [a-15] wherein X1 is nitro, fluorine, chlorine, bromine or iodine, the compound [a-20], and the compound [a-22] can also be produced by methods described in the following scheme. 
Wherein, R4, R5, R7, R17, X2, X3, X4, X12 and X13 are the same as defined above, R25 represents C1 to C6 alkyl which may be substituted such as methyl, ethyl, trifluoromethyl, trichloromethyl and the like: or C1 to C6 alkoxy which may be substituted such as methoxy, ethoxy and the like: or phenoxy which may be substituted such as phenoxy and the like.
 less than Process A13-1 greater than : A process for producing the compound [a-25] from the compound [a-24]
The compound [a-25] can be produced by reacting the compound [a-24] with the compound [b-2] in the presence of a base.
This reaction is conducted usually in the absence of a solvent or in a solvent, and the reaction temperature is usually from 0 to 200xc2x0 C., and the reaction time is usually from an instant to 24 hours.
Regarding the amounts of reagents to be used in the reaction, it is theoretical that the amount of the compound [b-2] is 1 mol and the amount of the base is 1 mol based on 1 mol of the compound [a-24], and the amounts thereof can be changed optionally depending on the reaction condition.
The base to be used includes organic bases such as pyridine, quinoline, benzyldimethylamine, phenetyldimethylamine, N-methylmorpholine, 1,8-diazabicyclo[5.4.0]undec-7-en, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,4-diazabicyclo[2.2.2]octane, 4-dimethylaminopyridine, N,N-dimethylaniline, N,N-diethylaniline, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, diisopropylethylamine and the like, and inorganic bases such as lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydride, potassium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide and the like.
Examples of the solvent to be used include aliphatic hydrocarbons such as n-hexane, n-heptane, ligroin, cyclohexane, petroleum ether and the like; aromatic hydrocarbons such as benzene, toluene, xylene and the like; aromatic halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, benzotrifluoride and the like; ethers such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diglyme and the like; ketones such as acetone, 2-butanone, methyl isobutyl ketone and the like; esters such as ethyl formate, ethyl acetate, butyl acetate, diethyl carbonate and the like; nitro compounds such as nitromethane, nitrobenzene and the like; nitriles such as acetonitrile, isobutyronitrile and the like; acid amides such as N,N-dimethylformamide, N,N-dimethylacetamide and the like; sulfur compounds such as dimethyl sulfoxide, sulfolane and the like; or mixtures thereof.
This reaction may sometimes be accelerated by using a catalyst. As the catalyst, copper iodide, copper bromide, copper chloride, copper powder and the like are listed, and the amount of the catalyst used in the reaction is from 0.0001 to 0.1 mol based on 1 mol of the compound [a-24], and the amounts thereof can be changed optionally depending on the reaction condition.
After completion of the reaction, an intended material can be obtained, for example, by the following operation 1) or 2).
1) A reaction solution is poured into water, this is extracted with an organic solvent, and the resulted organic layer is dried and concentrated.
2) A reaction solution is concentrated itself, or, filtrated if necessary before the filtrate is concentrated.
Further, the intended material can also be purified by a procedure such as chromatography, re-crystallization and the like.
 less than Process A13-2 greater than : A process for producing the compound [a-26] from the compound [a-25]
The compound [a-26] can be produced, for example, by reducing the compound [a-25] using an iron powder in the presence of an acid in a solvent.
The reaction temperature of this reaction is usually from 0 to 200xc2x0 C., preferably from room temperature to the reflux temperature. The reaction time is usually from an instant to 24 hours.
Regarding the amounts of reagents to be used in the reaction, the amount of the iron powder is from 3 mol to excess and the amount of the acid is 1 to 10 mol based on 1 mol of the compound [a-25], and the amounts thereof can be changed optionally depending on the reaction condition.
As the acid to be used, acetic acid and the like are listed.
As the solvent to be used, there are listed, for example, water, acetic acid, ethyl acetate and the like or mixtures thereof.
After completion of the reaction, an intended material can be obtained by usual post-treatment such as by pouring a reaction solution in to water directly or after filtration and collecting the produced crystals by filtration, or, extracting with an organic solvent, neutralization, drying, concentration and the like.
The intended material can also be purified by a procedure such as chromatography, re-crystallization and the like.
 less than Process A13-3 greater than : A process for producing the compound [a-27] from the compound [a-26]
The compound [a-27] can be produced by i) diazotizing the compound [a-26] in a solvent, then, ii) subsequently, reacting the diazo compound with potassium iodide, copper (I) bromide, copper (I) chloride or hydroborofluoric acid in a solvent.
In the diazotization reaction of the first step, the reaction temperature is from xe2x88x9220 to 20xc2x0 C., and the reaction time is usually from an instant to 5 hours.
Regarding the amounts of reagents to be used in the reaction, it is theoretical that the amount of the diazotization agent is 1 mol based on 1 mol of the compound [a-26], and the amounts thereof can be changed optionally depending on the reaction condition.
As the diazotization agent to be used, nitrites such as sodium nitrite, potassium nitrite, isoamyl nitrite, t-butyl nitrite and the like, are listed.
As the solvent, there are listed, for example, acetonitrile, hydrobromic acid, hydrochloric acid, sulfuric acid, water and the like or mixtures thereof.
The reaction solution after completion of the reaction is used as it is in the following reaction.
In the reaction of the second step, the reaction temperature is from 0 to 80xc2x0 C., and the reaction time is usually from an instant to 24 hours.
Regarding the amounts of reagents to be used in the reaction, each amount of potassium iodide, copper (I) bromide, copper (I) chloride or hydroborofluoric acid is from 1 to 3 mol based on 1 mol of the compound [a-26], and the amounts thereof can be changed optionally depending on the reaction condition. When copper [I] bromide is used, the reaction can also be conducted in the presence of copper (II) bromide, and when copper (I) chloride is used, the reaction can also be conducted in the presence of copper (II) chloride.
As the solvent to be used, there are listed, for example, acetonitrile, diethyl ether, t-butyl methyl ether, hydrobromic acid, hydrochloric acid, sulfuric acid, water and the like or mixtures thereof.
After completion of the reaction, an intended material can be obtained by usual post-treatment such as by collecting the produced crystals by filtration (if necessary, by adding water), or, extracting with an organic solvent, concentration and the like.
The intended material can also be purified by a procedure such as chromatography, re-crystallization and the like.
Further, this reaction is not limited to the above-mentioned methods, and production can also be conducted by reacting the compound [a-26] with the diazotizing agent in a solvent (for example, acetonitrile, diethyl ether, t-butyl methyl ether, hydrobromic acid, hydrochloric acid, sulfuric acid, water or mixtures thereof) in the presence of potassium iodide, copper (I) bromide, copper (I) chloride or hydroborofluoric acid. When copper [I] bromide is used, the reaction can also be conducted in the presence of copper (II) bromide, and when copper (I) chloride is used, the reaction can also be conducted in the presence of copper (II) chloride.
 less than Process A13-4 greater than : A process for producing the compound [a-28] from the compound [a-27]
The compound [a-28] can be produced by reacting the compound [a-27] with the compound [IV] in the presence of a base.
This reaction is conducted usually in a solvent, and the reaction temperature is usually from 0 to 200xc2x0 C., and the reaction time is usually from an instant to 72 hours.
Regarding the amounts of reagents to be used in the reaction, it is theoretical that the amount of the compound [IV] is 1 mol and the amount of the base is 1 mol based on 1 mol of the compound [a-27], and the amounts thereof can be changed optionally depending on the reaction condition.
The base to be used includes organic bases such as pyridine, quinoline, benzyldimethylamine, phenetyldimethylamine, N-methylmorpholine, 1,8-diazabicyclo[5.4.0]undec-7-en, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,4-diazabicyclo[2.2.2]octane, 4-dimethylaminopyridine, N,N-dimethylaniline, N,N-diethylaniline, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, diisopropylethylamine and the like, and inorganic bases such as lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydride, potassium hydride and the like.
Examples of the solvent to be used include aliphatic hydrocarbons such as n-hexane, n-heptane, ligroin, cyclohexane, petroleum ether and the like; aromatic hydrocarbons such as benzene, toluene, xylene and the like; aromatic halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, benzotrifluoride and the like; ethers such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diglyme and the like; ketones such as acetone, 2-butanone, methyl isobutyl ketone and the like; esters such as ethyl formate, ethyl acetate, butyl acetate, diethyl carbonate and the like; nitriles such as acetonitrile, isobutyronitrile and the like; acid amides such as N,N-dimethylformamide, N,N-dimethylacetamide and the like; sulfur compounds such as dimethyl sulfoxide, sulfolane and the like; or mixtures thereof.
After completion of the reaction, an intended material can be obtained, for example, by the following operation 1) or 2).
1) A reaction solution is poured into water, this is extracted with an organic solvent, and the resulted organic layer is dried and concentrated.
2) A reaction solution is concentrated itself, or, filtrated if necessary before the filtrate is concentrated.
Further, the intended material can also be purified by a procedure such as chromatography, re-crystallization and the like.
 less than Process A13-5 greater than : A process for producing the compound [a-28] from the compound [a-25]
The compound [a-28] wherein X13 is nitro can be produced by reacting the compound [a-25] with the compound [IV] in the presence of a base.
This reaction is conducted usually in a solvent, and the reaction temperature is usually from 0 to 200xc2x0 C., and the reaction time is usually from an instant to 72 hours.
Regarding the amounts of reagents to be used in the reaction, it is theoretical that the amount of the compound [IV] is 1 mol and the amount of the base is 1 mol based on 1 mol of the compound [a-25], and the amounts thereof can be changed optionally depending on the reaction condition.
The base to be used includes organic bases such as pyridine, quinoline, benzyldimethylamine, phenetyldimethylamine, N-methylmorpholine, 1,8-diazabicyclo[5.4.0]undec-7-en, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,4-diazabicyclo[2.2.2]octane, 4-dimethylaminopyridine, N,N-dimethylaniline, N,N-diethylaniline, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, diisopropylethylamine and the like, and inorganic bases such as lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydride, potassium hydride and the like.
Examples of the solvent to be used include aliphatic hydrocarbons such as n-hexane, n-heptane, ligroin, cyclohexane, petroleum ether and the like; aromatic hydrocarbons such as benzene, toluene, xylene and the like; aromatic halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, benzotrifluoride and the like; ethers such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diglyme and the like; ketones such as acetone, 2-butanone, methyl isobutyl ketone and the like; esters such as ethyl formate, ethyl acetate, butyl acetate, diethyl carbonate and the like; nitriles such as acetonitrile, isobutyronitrile and the like; acid amides such as N,N-dimethylformamide, N,N-dimethylacetamide and the like; sulfur compounds such as dimethyl sulfoxide, sulfolane and the like; or mixtures thereof.
After completion of the reaction, an intended material can be obtained, for example, by the following operation 1) or 2). 
1) A reaction solution is poured into water, this is extracted with an organic solvent, and the resulted organic layer is dried and concentrated.
2) A reaction solution is concentrated itself, or, filtrated if necessary before the filtrate is concentrated.
Further, the intended material can also be purified by a procedure such as chromatography, re-crystallization and the like.
(Intermediate Production Method 14)
The compound [III] wherein W is oxygen can also be produced by a method described in the following scheme. 
Wherein, R1, R2, R6, X1, X2, X3, X4 and Y are the same as defined above, R23 represents formyl, alkylcarbonyl which may be substituted such as acetyl and the like, or alkoxycarbonyl which may be substituted such as methoxycarbonyl and the like, and R24 represents hydrogen, alkyl which may be substituted such as methyl and the like, or alkoxy which may be substituted such as methoxy.
(Intermediate Production Method 15)
The compound [III] wherein X4 is hydrogen, fluorine, chlorine, bromine or iodine can also be produced by a method described in the following scheme. 
Wherein, R1, R2, R6, R16, W, X1, X2, X3, X12 and Y are the same as defined above.
(Intermediate Production Method 16)
Compounds [a-25] and [a-27] wherein R25 is defined as R20 can also be produced by a method described in the following scheme. 
Wherein, R16, R17, R20, X2, X3, X4 and X13 are the same as defined above.
The compound [a-42] can be produced, from the compound [a-41] according to a method described in Protective Groups in Organic Synthesis (published by A Wiley-Interscience publication) using boron tribromide, HBr/acetic acid, conc. hycrochloric acid or conc. sulfuric acid and the like.
Amount of reagent: from 1 mol to excess based on 1 mol of the compound [a-41]
Solvent: aromatic hydrocarbons such as benzene, toluene and the like, halogenated aliphatic hydrocarbons such as methylene chloride, chloroform and the like, halogenated aromatic hydrocarbons such as chlorobenzene and the like, or the mixture thereof.
Reaction Temperature: from xe2x88x9220xc2x0 C. to reflux temperature
Reaction Time: from an instant to 48 hours
After completion of the reaction, an intended material can be obtained by a post-treatment operation such as by pouring a reaction solution into water or adding an acid such as conc. hydrochloric acid and the like to a reaction solution and collecting the deposited crystals by filtration, or, extracting a reaction solution with an organic solvent and drying and concentrating the organic layer, or, concentrating a reaction solution itself, and the like. This compound can also be purified by an operation such as re-crystallization, chromatography and the like.
In the case of the compound [a-41) wherein R16 is benzyl which may be substituted, the compound [a-42] can also be produced from the compound [a-41] by hydrogenation in the presence of a catalyst.
This reaction is usually conducted in a solvent, the reaction temperature is usually from xe2x88x9220 to 150xc2x0 C., preferably from 0 to 50xc2x0 C. The reaction time is usually from an instant to 48 hours.
This reaction can also be conducted under pressure, and the reaction is preferably conducted under a pressure of 1 to 5 atom.
The amount of the catalyst used in this reaction is from 0.001 to 100% by weight based on the compound [a-41], As the catalyst to be used in the reaction, anhydrous palladium/carbon, water-containing palladium/carbon, platinum oxide and the like are listed.
The solvent includes carboxylic acids such as formic acid, acetic acid, propionic acid and the like, esters such as ethyl formate, ethyl acetate, butyl acetate, diethyl carbonate and the like; ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and the like; alcohols such as methanol, ethanol, propanol, isopropanol, butanol, t-butanol, amyl alcohol, isoamyl alcohol, t-amyl alcohol and the like; water, or mixtures thereof and the like.
After completion of the reaction, an intended material can be obtained by a usual post-treatment operation such as by filtrating a reaction solution before concentrating the solution itself, and the like. The intended material can also be purified by a procedure such as chromatography, re-crystallization and the like.
The compound [XXXXII] can be produced, for example, by a method described in WO98/08824 or a method according to the method described in this publication, and the compound [XXXXI], the compound [XXI], the compound [XXIV], the compound [XX] and the compound [XXV] can be produced by known methods or commercially available products can be used.
The present compounds have excellent herbicidal activity and some of them can exhibit excellent selectivity between crops and weeds. In other words, the present compounds have herbicidal activity against various weeds which may cause some trouble in the foliar treatment and soil treatment on upland fields, such as listed below.
Onagraceous weeds::
large-flowered eveningprimrose (Oenothera erythrosepala), cutleaf eveningprimrose (Oenothera laciniata),
Ranunculaceous weeds:
roughseeded buttercup (Ranunculus muricatus), hairy buttercup (Ranunculus sardous)
Polygonaceous weeds:
wild buckwheat (Polygonum convolvulus), pale smartweed (Polygonum lapathiolium), Pennsylvania smartweed (Polygonum pensylvanicum), ladysthumb (Polygonum persicaria), curly dock (Rumex crispus), broadleaf dock (Rumex obtusifolius), Japanese knotweed (Polygonum cuspidatum)
Portulacaceous weeds:
common purslane (Portulaca oleracea)
Caryophyllaceous weeds:
common chickweed (Stellaria media), sticky chickweed (Cerastium glomeratum)
Chenopodiaceous weeds:
common lambsquarters (Chenopodium album), kochia (Kochia scoparia)
Amaranthaceous weeds:
redroot pigweed (Amaranthus retroflexus), smooth pigweed (Amaranthus hybridus)
Cruciferous (brassicaceous) weeds:
wild radish (Raphanus raphanistrum), wild mustard (Sinapis arvensis), shepherdpurse (Capsella bursa-pastoris), virginia pepperweed (Lepidium virginicum)
Leguminous (fabaceous) weeds:
hemp sesbania (Sesbania exaltata), sicklepod (Cassia obtusifolia), Florida beggarweed (Desmodium tortuosum), white clover (Trifolium repens), common vetch (Vicia sativa), black medik (Medicago lupulina)
Malvaceous weeds:
velvetleaf (Abutilon theophrasti), prickly sida (Sida spinosa)
Violaceous weeds:
field pansy (Viola arvensis), wild pansy (Viola tricolor)
Rubiaceous weeds:
catchweed bedstraw (cleavers) (Galium aparine)
Convolvulaceous weeds:
ivyleaf morningglory (Ipomoea hederacea), tall morningglory (Ipomoea purpurea), entireleaf morningglory (Ipomoea hederacea var. integriuscula), pitted morningglory (Ipomoea lacunosa), field bindweed (Convolvulus arvensis)
Labiate weeds:
red deadnettle (Lamium purpureum), henbit (Lamium amplexicaule)
Solanaceous weeds:
jimsonweed (Datura stramonium), black nightshade (Solanum nigrum)
Scrophulariaceous weeds:
birdseye speedwell (Veronica persica), corn speedwell (Veronica arvensis), ivyleaf speedwell (Veronica hederaefolia)
Composite weeds:
common cocklebur (Xanthium pensylvanicum), common sunflower (Helianthus annuus), wild camomille (Matricaria chamomilla), scentless chamomile (Matricaria perforata or inodora), corn marigold (Chrysanthemum segetum), pineappleweed (Matricaria matricarioides), common ragweed (Ambrosia artemisiifolia), giant ragweed (Ambrosia trifida), horseweed (Erigeron canadensis), Japanese mugwort (Artemisia princeps), tall goldenrod (Solidago altissima), common dandelion (Taraxacum officinale)
Boraginaceous weeds:
forget-me-not (Myosotis arvensis)
Asclepiadaceous weeds:
common milkweed (Asclepias syriaca)
Euphorbiaceous weeds:
sun spurge (Euphorbia helioscopia), spotted spurge (Euphorbia maculata)
Geraniaceous weeds:
Carolina geranium (Geranium carolinianum)
Oxalidaceous weeds:
pink woodsorrel (Oxalis corymbosa)
Cucurbitaceous weeds:
burcucumber (Sicyos angulatus)
Graminaceous weeds:
barnyardgrass (Echinochloa crus-galli), green foxtail (Setaria viridis), giant foxtail (Setaria faberi), large crabgrass (Digitaria sanguinalis), Southern Crabgrass (Digitaria ciliaris), goosegrass (Eleusine indica), annual bluegrass (Poa annua), blackgrass (Alopecurus myosuroides), wild oat (Avena fatua), johnsongrass (Sorghum halepense), quackgrass (Agropyron repens), downy brome (Bromus tectorum), bermudagrass (Cynodon dactylon), fall panicum (Panicum dichotomiflorum), Texas panicum (Panicum texanum), shattercane (Sorghum vulgare), water foxtail (Alopecurus geniculatus)
Commelinaceous weeds:
common dayflower (Commelina communis)
Equisetaceous weeds:
field horsetail (Equisetum arvense)
Cyperaceous weeds:
rice flatsedge (Cyperus iria), purple nutsedge (Cyperus rotundus), yellow nutsedge (Cyperus esculentus)
Furthermore, some of the present compounds exhibit no significant phytotoxicity on the main crops such as corn (Zea mays), wheat (Triticum aestivum), barley (Hordeum vulgare), rice (Oryza sativa), sorghum (Sorghum bicolor), soybean (Glycine max), cotton (Gossypium spp.), sugar beet (Beta vulgaris), peanut (Arachis hypogaea), sunflower (Helianthus annuus), and canola (Brassica napus); horticultural crops such as flowers and ornamental plants; and vegetable crops. The present compounds can also attain the effective control of various weeds which may cause some trouble in the no-tillage cultivation of soybean (Glycine max), corn (Zea mays), wheat (Triticum aestivum), and other crops. Furthermore, some of the present compounds exhibit no significant phytotoxicity on the crops.
The present compounds also have herbicidal activity against various weeds which may cause some trouble in the flooding treatment on paddy fields, such as listed below.
Graminaceous weeds:
barnyardgrass (Echinochloa oryzicola)
Scrophulariaceous weeds:
common falsepimpernel (Lindernia procumbens)
Lythraceous weeds:
Indian toothcup (Rotala indica), red stem (Ammannia multiflora)
Elatinaceous weeds:
waterwort (Elatine triandra)
Cyperaceous weeds:
smallflower umbrella sedge (Cyperus difformis), hardstem bulrush (Scirpus juncoides), needle spikerush (Eleocharis acicularis), water nutgrass (Cyperus serotinus), water chestnut (Eleocharis kuroguwai)
Pontederiaceous weeds:
monochoria (Monochoria vaginalis)
Alismataceous weeds:
arrowhead (Sagittaria pygmaea), arrowhead (Sagittaria trifolia), waterplantain (Alisma canaliculatum)
Potamogetonaceous weeds:
roundleaf pondweed (Potamogeton distinctus)
Potamogetonaceous weeds:
roundleaf pondweed (Potamogeton distinctus)
Umbelliferous weeds:
watercelery sp. (Oenanthe javanica)
Furthermore, some of the present compounds exhibit no significant phytotoxicity on transplanted paddy rice.
The present compounds can also attain the control of a wide variety of weeds which are growing or will grow in the orchards, grasslands, lawns, forests, waterways, canals, or other non-cultivated lands in which weed controlling is necessiated such as levee, riverbed, roadside, railroad, green field of park, ground, parking, airport, industrial place (ex. factory, storage equipement), fallow land, vacant lot, and the like. The present compounds also have herbicidal activity against various aquatic weeds, such as water hyacinth (Eichhornia crassipes), which are growing or will grow at the waterside such as rivers, canals, waterways or reservoir.
The present compounds have substantially the same characteristics as those of the herbicidal compounds disclosed in the published specification of International Patent Application, WO95/34659. In the case where crops with tolerance imparted by introducing a herbicide tolerance gene described in the published specification are cultivated, the present compounds can be used at larger rates than those used when ordinary crops without tolerance are cultivated, which makes it possible to control other unfavorable weeds more effectively.
When the present compounds are used as the active ingredients of herbicides, they are usually mixed with solid or liquid carriers or diluents, surfactants, and other auxiliary agents to give emulsifiable concentrates, wettable powders, flowables, granules, concentrated emulsions, water-dispersible granules, or other formulations These formulations may contain any of the present compounds as an active ingredient at an amount of 0.001 to 80% by weight, preferably 0.005 to 70% by weight, based on the total weight of the formulation.
The solid carrier or diluent which can be used may include, for example, fine powders or granules of the following materials: mineral matters such as kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, and calcite; organic substances such as walnut shell powder; water-soluble organic substances such as urea; inorganic salts such as ammonium sulfate; and synthetic hydrated silicon oxide. The liquid carrier or diluent which can be used may include, for example, aromatic hydrocarbons such as methylnaphthalene, phenylxylylethane, and alkylbenzene (e.g., xylene); alcohols such as isopropanol, ethylene glycol, and 2-ethoxyethanol; esters such as phthalic acid dialkyl esters; ketones such as acetone, cyclohexanone, and isophorone; mineral oils such as machine oil; vegetable oils such as soybean oil and cottonseed oil; dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, N-methylpyrrolidone, and water.
The surfactant used for emulsification, dispersing, or spreading may include surfactants of the anionic type, such as alkylsulfates, alkylsulfonates, alkylarylsulfonates, dialkylsulfosuccinates, and phosphates of polyoxyethylene alkyl aryl ethers; and surfactants of the nonionic type, such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters.
The auxiliary agent may include lignin sulfonates, alginates, polyvinyl alcohol, gum arabic, CMC (carboxymethylcellulose), and PAP (isopropyl acid phosphate).
The present compounds are usually formulated as described above and then used for pre- or post-emergence soil, foliar, or flooding treatment of weeds. The soil treatment may include soil surface treatment and soil incorporation. The foliar treatment may include application over the plants and directed application in which a chemical is applied only to weeds so as to keep off the crop plants.
The present compounds may often exhibit the enhancement of herbicidal activity when used in admixture with other herbicides. They can also be used in admixture with insecticides, acaricides, nematocides, fungicides, bactericides, plant growth regulators, fertilizers, and soil conditioners.
Examples of the herbicide which can be used in admixture with the present compounds are atrazine, cyanazine, dimethametryn, metribuzin, prometryn, simazine, simetryn, chlorotoluron, diuron, fluometuron, isoproturon, linuron, methabenzthiazuron, propanil, bentazone, bromoxynil, ioxynil, pyridate, butamifos, dithiopyr, ethalfluralin, pendimethalin, thiazopyr, trifluralin, acetochlor, alachlor, butachlor, diethatyl-ethyl, dimethenamid, fluthiamide, mefenacet, metolachlor, pretilachlor, propachlor, cinmethylin, acifluorfen, acifluorfen-sodium, benzfendizone, bifenox, butafenacil, chlomethoxynil, fomesafen, lactofen, oxadiazon, oxadiargyl, oxyfluorfen, carfentrazone-ethyl, fluazolate, flumiclorac-pentyl, flumioxazine, fluthiacet-methyl, isopropazol, sulfentrazone, thidiazimin, azafenidin, pyraflufen-ethyl, cinidon-ethyl, difenzoquat, diquat, paraquat, 2,4-D, 2,4-DB, clopyralid, dicamba, fluroxypyr, MCPA, MCPB, mecoprop, quinclorac, triclopyr, azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cloransulam-methyl, cyclosulfamuron, diclosulam, ethoxysulfuron, flazasulfuron, flucarbazone, flumetsulam, flupyrsulfuron, halosulfuron-methyl, imazosulfuron, indosulfuron, metosulam, metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron-methyl, procarbazone-sodium, prosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfometuron-methyl, sulfosulfuron, triasulfuron, tribenuron-methyl, tritosulfuron, thifensulfuron-methyl, triflusulfuron-methyl, pyribenzoxim, bispyribac-sodium, pyriminobac-methyl, pyrithiobac-sodium, imazameth, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, tepraloxydim, alloxydim-sodium, clethodim, clodinafop-propargyl, dihalofop-butyl, dichlofop-methyl, fenoxaprop-ethyl, fenoxaprop-p-ethyl, fluazifop-buthyl, fluazifop-p-butyl, haloxyfop-methyl, quizalofop-p-ethyl, sethoxydim, tralkoxydim, diflufenican, flurtamone, norflurazone, benzofenap, isoxaflutole, pyrazolate, pyrazoxyfen, sulcotrione, clomazone, mesotrione, isoxachlortole, bialaphos, glufosinate-ammonium, glyphosate, sulfosate, dichlobenil, isoxaben, benthiocarb, butylate, dimepiperate, EPTC, esprocarb, molinate, pyributicarb, triallate, bromobutide, DSMA, MSMA, cafenstrol, daimron, epoprodan, flupoxam, metobenzuron, pentoxazone, piperophos, triaziflam, beflubutamid, benzobicyclon, clomeprop, fentrazamide, flufenacet, florasulam, indanofan, isoxadifen, mesotrione, naploanilide, oxaziclomefone, pethoxyamid, phnothiol, pyridafol.
The above compounds are described in the catalog of Farm Chemicals Handbook, 1995 (Meister Publishing Company); AG CHEM NEW COMPOUND REVIEW, VOL. 13, 1995, VOL. 15, 1997, VOL. 16, 1998 or, VOL. 17, 1999 (AG CHEM INFORMATION SERVICES); or Josouzai Kenkyu Souran (Hakuyu-sha).
When the present compounds are used as the active ingredients of herbicides, the application amount, although it may vary with the weather conditions, formulation types, application times, application methods, soil conditions, crops to be protected, weeds to be controlled, and other factors, is usually in the range of 0.01 to 20,000 g, preferably 1 to 12,000 g, per hectare. In the case of emulsifiable concentrates, wettable powders, flowables, concentrated emulsions, water-dispersible granules, or other similar formulations, they are usually applied after diluted in their prescribed amounts with water (if necessary, containing an adjuvant such as a spreading agent) at a ratio of 10 to 1000 liters per hectare. In the case of granules or some types of flowables, they are usually applied as such without any dilution.
The adjuvant which can be used, if necessary, may include, in addition to the surfactants as described above, polyoxyethylene resin acids (esters), lignin sulfonates, abietates, dinaphthylmethanedisulfonates, crop oil concentrates, and vegetable oils such as soybean oil, corn oil, cottonseed oil, and sunflower oil.
The present compounds can also be used as the active ingredients of harvesting aids such as defoliants and desiccants for cotton (Gossipyum spp.), and desiccants for potato (Solanum tuberosum). In these cases, the present compounds are usually formulated in the same manner as the case where they are used as the active ingredients of herbicides, and used alone or in admixture with other harvesting aids for foliar treatment before the harvesting of crops.
The following production examples, formulation examples and test examples and the like will illustrate the present invention further in detail below, but do not limit the scope of the invention.
First, production examples of present compounds and production examples of intermediates will be shown. The compound numbers of present compounds correspond to numbers described in Tables 1 to 5 described below.